Van Dam made his WWF television on the July 9, 2001 episode of Raw in Atlanta, Georgia as a heel, by attacking WWF wrestlers Kane and Chris Jericho. Despite being a heel, Van Dam was popular with the WWF fans. After defeating Jeff Hardy for the WWF Hardcore Championship at Invasion, Van Dam became one of the most "over" members of the Alliance and even challenged Alliance leader Stone Cold Steve Austin for the WWF Championship including a triple threat match at No Mercy. Van Dam lost the Hardcore Title to Hardy on the August 13 episode of Raw, but regained the title from Hardy at SummerSlam. At Survivor Series on November 18, Van Dam and four other Alliance members faced five WWF wrestlers in a Winner Take All match. Team WWF won, and the members of the Alliance were fired; however, as he held the Hardcore Championship, Van Dam was able to retain his job.
Van Dam became a face but lost the Hardcore Championship to The Undertaker at Vengeance. He then entered into a rivalry with William Regal over Regal's Intercontinental title. On the February 25 episode of Raw, Van Dam defeated Lance Storm and Big Show in a triple threat match to become the #1 contender to the Intercontinental title. At WrestleMania X8, RVD faced Regal for the Intercontinental title and won the match after he hit Regal with a Five-Star Frog Splash.
When the WWF was divided into two "brands", Raw and SmackDown! in 2002, Van Dam was drafted to the Raw brand as the fourth pick. After he defended his title successfully against Booker T, Eddie Guerrero returned to the WWF and attacked Van Dam. He started a feud with Eddie Guerrero over the Intercontinental title. At Backlash, Van Dam lost the Intercontinental Title to Guerrero. At Insurrextion, Van Dam and Guerrero had a rematch for the Intercontinental Title. Guerrero was disqualified after hitting the referee with the Intercontinental title; as a result, Van Dam won the match but not the title because a title cannot change hands by disqualification. At Judgment Day, Van Dam failed to win the Intercontinental Title in another rematch. The following night he defeated The Undertaker for the Undisputed Championship but authority figure Ric Flair restarted the match, which Van Dam then lost negating the title win. On the May 27 episode of Raw, Van Dam defeated Eddie Guerrero in a ladder match for the Intercontinental Title.
After facing each other in the final round of the King of the Ring tournament, Van Dam and Brock Lesnar began feuding with each other. Van Dam defended his Intercontinental Title against Lesnar twice and retained his title both times by disqualification. On July 21, 2002, Van Dam unified the WWE European Championship into the WWE Intercontinental Championship after he defeated European Champion Jeff Hardy in a title unification ladder match. As a result, the European title was abandoned. On the July 29 episode of Raw, Van Dam lost the Intercontinental title to Chris Benoit.
At SummerSlam, Van Dam won his third WWE Intercontinental Championship by defeating Benoit in a rematch for the title. As Benoit brought the title to SmackDown when he switched brands shortly after winning it, RVD brought the Intercontinental Title back to Raw. On the August 26 episode of Raw, Van Dam also unified the WWE Hardcore Championship into the WWE Intercontinental Championship by defeating Hardcore Champion Tommy Dreamer in a hardcore title unification match. As a result, the WWE Hardcore Championship was abandoned. On the September 9 episode of Raw, Van Dam became the number one contender to the World Heavyweight Championship by defeating Chris Jericho, Jeff Hardy, and Big Show in a fatal four-way elimination match.
Van Dam started feuding with the World Heavyweight Champion Triple H. On the September 16 episode of Raw, Van Dam lost the Intercontinental title to Chris Jericho after interference by Triple H. At Unforgiven, Van Dam faced Triple H for the World Heavyweight Championship. Due to Ric Flair's interference, Van Dam lost the match. At No Mercy, Van Dam got his revenge on Flair by defeating him. At Survivor Series, Van Dam participated in the first-ever Elimination Chamber match for Triple H's World Heavyweight Championship, but it was won by Shawn Michaels. During the match Rob Van Dam performed a Five-Star Frog Splash off of one of the pods/chambers onto Triple H accidentally landing with his knee onto HHH's throat.
Van Dam appeared on the World Heavyweight Championship scene and also formed a tag team with Kane in October 2002. Van Dam defeated Jericho and Booker T in a Triple Threat match to become the number one contender for the World Heavyweight Championship. On the November 25 episode of Raw, Van Dam faced Michaels for the World Heavyweight Championship. Michaels was disqualified after Triple H hit RVD with a Pedigree. On the December 2 episode of Raw, Van Dam lost to Triple H in a #1 contender's match with World Heavyweight Champion Shawn Michaels acting as the special guest referee.
In 2003, Rob Van Dam continued to team up with Kane. RVD participated in the Royal Rumble, and was one of the final five participants before being tricked and eliminated by his tag team partner Kane. The two faced Lance Storm and William Regal at No Way Out for the World Tag Team Championship but failed to win the title when Kane mistakenly chokeslammed RVD. On the March 31 episode of Raw, Van Dam and Kane defeated World Tag Team Champions Lance Storm and Chief Morley and The Dudley Boyz in a 3-way elimination tag team match to win the World Tag Team Championship. At Backlash, Van Dam and Kane retained the titles against The Dudley Boyz with Morley as the special guest referee. At Insurrextion, Van Dam and Kane defended the World Tag Team title successfully against La Résistance, before losing the title to La Résistance at Bad Blood.
After Kane was forced to take his mask off when he lost to Triple H, he turned heel, and the team with RVD dissolved. The two then started feuding with each other. On the August 18 episode of Raw, Van Dam faced the Intercontinental Champion Christian for the title, but Kane interfered in the match and knocked Van Dam out after hitting him with a chair. Kane then took Van Dam to the backstage where he was restrained and was about to be set on fire. Kane changed his mind at the last minute, however, and said that he wasn't going to do what "they" want. Their rivalry led to a No Holds Barred match at SummerSlam, which Kane won. On the September 8 episode of Raw, the rivalry ended when Rob Van Dam defeated Kane, when Kane threw RVD through the Steel by mistake in a steel cage match. Eric Bischoff came out and restarted the match, saying RVD didn't escape through the door or climb out Bischoff ordered the referees to put Rob Van Dam's body back inside the cage Kane eventually hit a chokeslam from the side of the cage to pick up the victory.
In September 2003, Van Dam started feuding with both Christian and Chris Jericho over Christian's Intercontinental Title. On the September 15 episode of Raw, Van Dam faced Jericho in a number one contender's match for the title. The match ended in a double disqualification when Intercontinental Champion Christian interfered and hit both men with the title belt. At Unforgiven in a triple threat match between Jericho, Christian, and Van Dam, Christian retained his title. Van Dam, however, defeated Christian in a ladder match on the September 29 episode of Raw to win the Intercontinental Championship for a fourth time.
Van Dam entered into a rivalry with Chris Jericho in October 2003, and the two faced each other in several tag team matches. On the October 27 episode of Raw, Van Dam lost the Intercontinental title to Jericho. Van Dam reached the ropes when the challenger had him in the Walls of Jericho, but Eric Bischoff distracted the referee while Jericho dragged the champion back into the middle of the ring. Van Dam submitted and Jericho became the new champion. Austin came out and immediately ordered Jericho to face Van Dam in a rematch inside the Steel Cage for the title. Van Dam won the rematch and his fifth Intercontinental Championship.
At Survivor Series, Van Dam was pinned by Randy Orton during his traditional elimination match. As a result, Orton and Van Dam started feuding with each other over Van Dam's Intercontinental title. Van Dam lost the Intercontinental title to Orton at Armageddon after interference from Ric Flair. Van Dam went on to feud with both Orton and Evolution. On the January 12, 2004 episode of Raw, Van Dam faced Orton in a rematch for the Intercontinental title but lost the match.
Van Dam formed a tag team with Booker T. The two teamed for the first time on the January 19 episode of Raw when they defeated Christian and Matt Hardy to qualify for a battle royal where the winner of the battle royal would get the #30 spot in the 2004 Royal Rumble match. On the February 16 episode of Raw, Booker T and Van Dam defeated Evolution members Ric Flair and Batista to win the World Tag Team Championship. At WrestleMania XX, Booker and Van Dam defended the World Tag Team Championship in a fatal four-way elimination tag team match against the Dudley Boyz, La Résistance, and the team of Mark Jindrak and Garrison Cade. On the March 22 episode of Raw, Booker T and Van Dam lost the World Tag Team Championship back to Evolution.
On March 22, Van Dam was drafted from Raw to SmackDown!. He made his SmackDown! debut on March 25 defeating Charlie Haas. Van Dam and Rey Mysterio began a feud with the Dudley Boyz, defeating them at Judgment Day. In June, Van Dam left the tag team division and began a pursuit for the United States Championship. At The Great American Bash, John Cena defended the title against RVD, Booker T, and René Duprée in a fatal four-way match and retained his championship. On the July 1 episode of SmackDown!, Van Dam and Duprée lost to Booker in a number one contender's triple threat match. Four weeks later, Van Dam participated in an 8-way elimination match for the vacant US Championship, and was the last man to be eliminated by eventual winner Booker.
Van Dam began teaming up with Mysterio again in the summer and feuded with René Duprée and Kenzo Suzuki. At No Mercy, Van Dam and Mysterio failed to win the Tag Team Championship from Dupree and Suzuki. On the December 9 episode of SmackDown!, Van Dam and Mysterio defeated Duprée and Suzuki to win the WWE Tag Team Championship, and retained the title in a rematch at Armageddon. In January 2005, Van Dam suffered a knee injury. To explain his absence, the Basham Brothers (Doug and Danny) defeated Mysterio and Van Dam for the Tag Team Championship, in a fatal four-way elimination tag team match on the January 13 episode of SmackDown!, "injuring" Van Dam in the process. On January 27, Van Dam underwent reconstructive knee surgery under Dr. James Andrews to repair a torn anterior cruciate ligament and meniscus.
While recuperating, Van Dam made an appearance at the ECW reunion pay-per-view ECW One Night Stand. Accompanied by Bill Alfonso and sporting a knee brace, Van Dam delivered a worked shoot promo, standing up for ECW and criticizing the way he had been booked in WWE, until he was attacked by Rhyno. He was saved by Sabu, who defeated Rhyno in an impromptu match. Despite his injury, Van Dam got physically involved in the match, hitting Rhyno with a chairshot and giving him a Chair Surf. Van Dam, while still healing, was drafted back to the Raw brand in the 2005 Draft Lottery. He was introduced to Raw by Carlito, who insulted Van Dam before attacking him and assaulting his knee. Van Dam made his return to the ring over six months later at the Royal Rumble. He gained revenge on Carlito by eliminating him, but was in turn inadvertently eliminated by Rey Mysterio. On the February 6 episode of Raw, Van Dam defeated Carlito in the first round of the 2006 Road to WrestleMania Tournament, but lost in the final round to Triple H, in a triple threat match, which also featured Big Show. Later, Van Dam defeated Trevor Murdoch to qualify for the Money in the Bank ladder match. Van Dam went on to win the match, thus earning himself a guaranteed shot at either the WWE Championship or World Heavyweight Championship at any time within the subsequent year. Following the ladder match, Shelton Benjamin challenged Van Dam to put his Money in the Bank opportunity on the line in a match. Van Dam countered by requesting a match for Benjamin's Intercontinental Championship. One week later, both Van Dam and Benjamin picked mystery opponents for one another, with the loser placing their respective prize on the line in a bout at Backlash on April 30. Benjamin lost to the returning Charlie Haas, while Van Dam was defeated by all five members of the Spirit Squad. As a result, both the Intercontinental Championship and the Money in the Bank title shot were contested at Backlash. Van Dam went on to win both prizes, before dropping the Intercontinental title back to Benjamin on the May 15 episode of Raw.
On May 29, Van Dam was selected by Paul Heyman to be drafted from Raw to WWE's new ECW brand. At One Night Stand, Van Dam cashed in his Money in the Bank Contract, and defeated John Cena to win the WWE Championship. After two referees were knocked out, Edge appeared from underneath the ring to attack Cena, spearing him through a table. Van Dam then hit a Five Star Frog Splash and the pinfall was counted by Paul Heyman, who suddenly ran down the aisle. On the following episode of Raw, Vince McMahon confirmed that the title change was official, due to the match being held under "extreme rules". For the past few weeks, Heyman had hinted that the WWE Championship would be "rechristened" the ECW World Heavyweight Championship when Van Dam won. On the debut of ECW on Sci Fi, Van Dam was awarded the reinstated ECW World Heavyweight Championship by Heyman. Van Dam, however, decided to defend the WWE Championship separately and simultaneously, joking that "this one spins". Thus, Van Dam became the first wrestler in history to hold both the WWE Championship and the ECW World Heavyweight Championship, and the only one to hold them at the same time. At Vengeance Van Dam defeated Edge to retain the WWE Championship despite interference by Lita. On the July 3 episode of Raw, Van Dam lost the WWE Championship to Edge in a triple threat match that also featured John Cena. The next night, on the July 4 episode of ECW, he lost the ECW World Heavyweight Championship to The Big Show after Heyman turned on him. Later on WWE.com, Heyman suspended Van Dam for 30 days without giving a reason; (in reality, WWE suspended Van Dam for 30 days as a result of his recent drug possession arrest).
He returned to television on August 8, attacking both Sabu and Kurt Angle during a match. His return to the ring came a week later, in a losing effort to Sabu in a ladder match for number one contendership to the ECW World Championship. Van Dam slowly worked his way back into the championship picture. In October, Van Dam defeated The Big Show in a non-title match to regain the number one contendership. Having the option to pick a date, Van Dam announced the title match would occur at December to Dismember. Heyman, however, had the option of picking the match type and announced that the main event would be a six-man Extreme Elimination Chamber match. At the event, Van Dam was the third participant eliminated. Later in December, Van Dam once again earned the number one contendership to the ECW World Championship, but this time by a fan poll. Van Dam got three matches against ECW World Champion Bobby Lashley, coming up short each time.
Rob Van Dam later joined the ECW Originals along with Sabu, Tommy Dreamer, and The Sandman. The ECW Originals began a feud with the New Breed (Elijah Burke, Kevin Thorn, Marcus Cor Von, and Matt Striker). The two teams faced off at WrestleMania 23 in a match which the ECW Originals won. After Vince McMahon won the ECW World Championship at Backlash, RVD and the other ECW Originals made statements on WWE.com about McMahon killing ECW. The ECW Originals all competed in a four way dance to decide who would take on McMahon the next week on ECW in a title match, which Van Dam won after a five-star frog splash on Sandman. Van Dam, however, had to face McMahon, Shane McMahon, and Umaga in a 3 on 1 handicap match, which Van Dam was unable to win.
Van Dam received a concussion during a match with Randy Orton. Orton further attacked Van Dam after the match due to the comments Van Dam made on WWE.com about the lack of respect Orton displayed towards Shawn Michaels, who also suffered a concussion at the hands of Orton. Van Dam once again faced Orton at One Night Stand, this time in a Stretcher match. Although it looked as if Orton was going to win again, Van Dam gave him a roundhouse kick to the head and was able to push the stretcher across the line for the win. Despite winning the match, Orton continued to attack Van Dam, ending with an elevated DDT off the barricade and onto the concrete floor. After the match, Van Dam left WWE due to a family issue, as his wife had recently been diagnosed with cancer. Van Dam made an unannounced return on the 15th Anniversary Raw in December 2007, squashing Santino Marella with a Five-Star Frog Splash. He soon returned in 2009 to participate in the Royal Rumble.
In April, 2013, Van Dam was spotted at the WWE Hall of Fame induction ceremony. He then told WWE.com in an interview he was at the event to support new inductee and former tag team partner Booker T. Later in the interview, when speaking about a possible WWE return, Van Dam stated “There’s always a chance.” On June 16, it was announced during a vignette at WWE's Payback pay-per-view event that Van Dam, who last appeared for WWE as a surprise entrant in the 2009 30-man Royal Rumble match, would be returning at Money in the Bank on July 14, 2013. On June 24 at Raw it was announced that Van Dam will compete in the Money in The Bank Ladder match for a WWE Championship contract. On July 14 at Money in the Bank, Van Dam returned to take part in the ladder match, but was unsuccessful as the match was won by Orton. The following night on Raw, Van Dam wrestled his first match on the show in six years, where he defeated Chris Jericho. Four days later, Van Dam wrestled his first SmackDown match in eight years, when he defeated Darren Young. Van Dam suffered his first loss since returning to WWE on the July 26 episode of SmackDown, when he was pinned by World Heavyweight Champion Alberto Del Rio in a non-title match. The following week on SmackDown, Van Dam was defeated by Christian in a three-way number one contenders match for Del Rio's World Heavyweight Championship, which also included Randy Orton. Three days later on Raw, Van Dam defeated Del Rio in a rematch. On the August 12 episode of Raw, Van Dam won a twenty-man battle royal, by last eliminating Mark Henry to become the number one contender to the United States Championship. After the match, Van Dam and Henry were confronted by The Shield (Dean Ambrose, Roman Reigns, and Seth Rollins), before the returning Big Show came to their aid. Four days later on SmackDown, Van Dam, Henry, and Show defeated the Shield in a six-man tag team match, with Van Dam pinning Ambrose for the win. Van Dam received his title shot on August 18, during the SummerSlam, where he defeated Ambrose via disqualification after Roman Reigns speared Van Dam, not winning the title as a result.
Van Dam then aligned himself Alberto Del Rio's former ring announcer Ricardo Rodriguez the following night on Raw, to feud with Del Rio. The following week on Raw, Van Dam, with Rodriguez in his corner, defeated Del Rio in a non-title match to earn a shot at his World Heavyweight Championship. The title match took place on September 15 at Night of Champions, where Van Dam won the match via disqualification, but did not win the title. Van Dam received another shot at the World Heavyweight Championship on October 6 at WWE Battleground, but was defeated by Del Rio in a Hardcore match. The following night it was announced that Van Dam has taking some time off. On April 7, 2014, RVD returned to Raw, defeating Damien Sandow. The following week on Raw Van Dam entered in Intercontinental Championship tournament, where he defeated Alberto Del Rio by pinfall in the first round, and then defeated Cesaro by countout in the second round, but lost in the final round to Bad News Barrett who won the tournament. At Extreme Rules, Van Dam faced Cesaro and Jack Swagger in a Triple Threat Elimination match which was won by Cesaro after pinning Van Dam last, who had pinned Swagger first. On the May 19 episode of Raw Van Dam won a Beat the Clock Challenge match by defeating Alberto Del Rio in the fastest time, to become the number one contender for the Intercontinental Championship at Payback. At the event Van Dam lost to the champion Bad News Barrett. At Money in the Bank Van Dam took part in the Money in the Bank Ladder match for the briefcase but the match was won by Seth Rollins. On July 1 edition of Main Event Van Dam was announced as a participant in a battle royal at Battleground for the vacant Intercontinental Championship, but he suffered an injury and couldn't compete. Van Dam returned to the ring on the August 4 edition of Raw where he was scheduled to compete against Seth Rollins in a Beat the Clock challenge match, but was switched with Heath Slater by the order of The Authority. Van Dam finished his current run with WWE at the August 26 Smackdown tapings, where he faced Seth Rollins in a losing effort. He then later returned to Raw at the 2014 Slammy Awards to announce the winner of the extreme moment of the year.