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Goldust debuted as a fan favorite in the World Wrestling Federation in late 1990, wrestling as Dustin Rhodes. In December 1990, Rhodes defeated Ted DiBiase in a televised ten-minute challenge match. On January 19, 1991 at the Royal Rumble, Rhodes and his father Dusty lost to Ted DiBiase and Virgil in a tag team bout, and left immediately after.

In September 1995, Rhodes returned to the World Wrestling Federation, wrestling as a villain nicknamed "the bizarre one" because of his somewhat spooky, very suggestive mannerisms and presence under the name Goldust. He deliberately attempted to creep out his opponents through lewd and flirtatious mind games. The character is portrayed as being obsessed with films and the color gold, as a pun of the Oscars Statuette. As Goldust, Rhodes wrestled and won his debut match on October 22, 1995 against Marty Jannetty at the In Your House 4 pay-per-view.

Goldust initially feuded with Razor Ramon, whom he stalked and sent messages to throughout late 1995. The feud culminated at the Royal Rumble on January 21, 1996, where Goldust defeated Ramon for the Intercontinental Championship due to interference from the 1-2-3 Kid. This match also marked the debut of his valet, Marlena. With a seductively nonchalant character, Marlena sat at ringside in a director's chair, advising Goldust while smoking a cigar. A rematch between Goldust and Ramon at WrestleMania XII was canceled after Ramon was suspended, with Goldust instead wrestling and losing to Roddy Piper in a non-title "Hollywood Backlot Brawl".

Goldust defended his Intercontinental Championship in bouts against Savio Vega and The Ultimate Warrior before losing to Ahmed Johnson at King of the Ring on June 23, 1996. In August 1996, Goldust briefly gained control over Mankind and feuded with The Undertaker. His attention soon turned to Marc Mero and his then wife Sable. Goldust and Marlena attempted to get Sable to join their team, but Mero won the feud and kept her by his side.

In the summer and fall of 1997, he joined other wrestlers in their conflict with The Hart Foundation, feuding in particular with Brian Pillman, to whom he lost the services of Marlena for thirty days. Just before the thirty days were up, Pillman died hours before Badd Blood of heart disease on October 5, 1997. In November 1997, Goldust split with Marlena and refused to cooperate with his Survivor Series teammates, which once again turned him into a heel. This led to a feud with Vader and the appearance of The Artist Formerly Known As Goldust, managed by Luna Vachon. He began mimicking fellow wrestlers with characters such as "Chynadust", "Dust Lovedust", "Dustydust", "Hunterdust", "Flashdust", "Sabledust", and "Vaderdust".

In early 1999, Goldust feuded with Al Snow, upon stealing Head, Snow's mascot, and The Blue Meanie, who had recently renamed himself "Bluedust" and adopted many of Goldust's mannerisms. After Goldust defeated Meanie at St. Valentine's Day Massacre, Meanie became Goldust's apprentice. After Ryan Shamrock became Goldust's valet, Meanie and Shamrock began vying for Goldust's attention. In the same time period, Goldust won the Intercontinental Championship again from Road Dogg and then lost it to The Godfather two weeks later.

On January 20, 2002, Goldust returned by taking part in the Royal Rumble. Shortly after returning, promos began airing for a few weeks of Goldust saying that there was a certain wrestler whose "star was shining brighter" than he'd like. He eventually revealed the person he was talking about was Rob Van Dam by attacking him on Raw. Van Dam defeated him in a singles match at No Way Out 2002. After the loss, he moved on to the hardcore division, where he won the Hardcore Championship on seven occasions.

When the World Wrestling Federation was renamed World Wrestling Entertainment and the roster was divided into two brands, Raw and SmackDown!, Goldust was assigned to the Raw brand, where he formed a tag team with Booker T. The duo engaged in numerous comedic vignettes, on one occasion hosting a segment titled Booker T and Goldust at the Movies and delivering reviews of The Scorpion King, a film starring The Rock. In May 2002, Booker joined the nWo, with Goldust's request to join the faction rejected. In June 2002, Booker was ejected from the nWo by Shawn Michaels, sparking a feud between the nWo and Booker and Goldust. Booker and Goldust went on to compete in the tag team division, winning the World Tag Team Championship at Armageddon before being forced to split up on the February 3, 2003 episode of Raw by Raw General Manager Eric Bischoff for failing to win back the World Tag Team Titles.

Following the dissolution of the tag team, Goldust developed a gimmick whereupon he contracted a stutter, as well as Tourette's-like symptoms (which continue to this day), upon receiving a shock from a Round Tube during an attack at the hands of Batista and Randy Orton. Goldust appeared sporadically thereafter, forming a tag team with Lance Storm in August 2003. In fall 2003, Booker T. began receiving mysterious, haunting messages for a few weeks from somebody. The messages only said "I remember". It was rumored that the messages would be from Goldust, which would have begun a feud between the two. Suddenly, the angle was never mentioned again on television and the company announced on their web site that they allowed his contract to expire in December 2003.

Goldust returned to World Wrestling Entertainment on October 31, 2005 repackaged as a heel as Jonathan Coachman enlisted him and Vader to attack Batista. Goldust and Vader unsuccessfully interfered in a Street Fight between Batista and Coachman on behalf of Coachman at Taboo Tuesday. Following the event, Goldust once again disappeared from television.

In January 2006, Goldust took part in the Royal Rumble match and was assigned once again to the Raw brand until he was released from his WWE contract on June 14, 2006 for no-showing an appearance.

On October 26, 2008, Goldust returned to the WWE and turned face on Cyber Sunday as part of the three choices (the other two being Roddy Piper and The Honky Tonk Man) that the fans could choose to face Santino Marella for the Intercontinental Championship. After Honky Tonk Man was chosen and won via disqualification, Goldust and Piper entered the ring and the three candidates fought Marella, afterwards celebrating together in the ring. The following night on Raw, Goldust appeared again with Piper and the Honky Tonk Man as guest commentators for Marella's match with Charlie Haas. The match ended when Goldust and Piper distracted Marella so that Honky Tonk Man could smash his guitar over Marella's head.

Goldust appeared on the celebration of the 800th episode of Raw on November 3, 2008, dancing alongside his father Dusty Rhodes, Lilian Garcia and several other wrestlers. Goldust finally made a full-time return on the Raw roster once again on the November 24, 2008 episode of Raw, where he defeated Santino Marella. Goldust participated in the 2009 Royal Rumble match and stared down his real-life half-brother, Cody Rhodes, but was eliminated by him later. Goldust participated at WrestleMania XXV as a lumberjack during the tag team championship unification match between The Colóns and John Morrison and The Miz.

On May 25, episode of Raw, Goldust teamed up with Hornswoggle in a tag team match, where they defeated Festus and The Brian Kendrick. Goldust then teamed with Hornswoggle on multiple occasions, mainly feuding with Kendrick, where they had many matches both on WWE Superstars and Raw.

The team of Goldust and Hornswoggle came to an end on June 29, 2009 when Goldust was traded to the ECW brand via a 15-man trade, marking the first time that he had been on another brand other than Raw. His debut match for the brand came on the July 14 episode of ECW, in which he lost to Zack Ryder. In the upcoming weeks, he started a feud with Sheamus leading to his first televised singles win in several months on Superstars against Sheamus pinning him using an inside cradle. After several weeks of feuding, Sheamus defeated Goldust in a "No Disqualifications" match on the September 1 episode of ECW on Syfy to end the feud.

Following this loss, he garnered his first number one contender's match for the ECW Championship on the September 15, 2009 episode of ECW on Syfy in a 10-Man Battle Royal where he was the seventh participant eliminated and Zack Ryder earning the title shot in the end. The September 29, 2009 episode of ECW on Syfy saw Goldust win his first match on ECW in an 8-Man Tag-Team match where Yoshi Tatsu pinned William Regal to score the win for their team. Goldust debuted a new finishing maneuver called the "Golden Age" on the October 22, 2009, episode of WWE Superstars, when he and Tommy Dreamer defeated Vladimir Kozlov and Ezekiel Jackson. On the November 10 episode of ECW on Syfy, Goldust won his first televised singles match on the ECW brand by pinning Paul Burchill. Goldust participated in an "ECW Homecoming" Match on the December 22 episode of ECW on Syfy to determine who will get an opportunity to challenge Christian for the ECW Championship, but was defeated by Vance Archer.

In early January, he teamed with Yoshi Tatsu and began a feud with ECW newcomers Trent Barreta and Caylen Croft. The duos exchanged victories in singles and tag team competition until the feud came to an end on the February 9 episode of ECW, when Goldust and Tatsu defeated Barreta and Croft in a match to determine the number one contenders to the Unified WWE Tag Team Championship. However, Goldust and Tatsu failed in capturing the titles on the final episode of ECW on Syfy. The team of Goldust and Yoshi Tatsu came to an end when Tatsu signed with the Raw brand after ECW on SyFy was cancelled.

On March 3, 2010, Goldust joined the SmackDown brand, making it the first time that Goldust had ever been officially on the SmackDown roster. He made his debut for the brand on the March 4 episode of Superstars in a losing effort against Chris Jericho. The following week on Superstars, he won his first match as a SmackDown star after defeating Mike Knox using his finishing move, the Final Cut, as well as beating William Regal also using the Final Cut soon afterwards. He appeared in a dark 26-man battle royal match at WrestleMania XXVI, but failed to win, although his past ally Yoshi Tatsu won.

As part of the 2010 WWE Supplemental Draft, Goldust was drafted back to the Raw brand. On the May 3 episode of Raw, Goldust made his re-debut for the brand in a backstage segment with the guest host for that week, Wayne Brady. In late September, a mysterious stalker was sending messages to Maryse and Ted DiBiase, but it was unsure who they were aimed at. On the October 4 episode of Raw, Goldust was revealed as the mystery stalker, but the messages were not directed to Maryse, but at DiBiase's Million Dollar Championship, which he then took.

During the season 2 finale of NXT on August 31, 2010, it was announced that Goldust would take part in NXT's third season as a Pro with Aksana as his Rookie. On the October 12 episode of NXT Goldust proposed to Aksana, who was facing deportation from the country, so she could stay in America. On the October 18 episode of Raw, DiBiase tried to reclaim his Million Dollar Championship after Goldust's match with Zack Ryder by attacking him, but he was unsuccessful in retrieving his belt. At Bragging Rights, DiBiase defeated Goldust, but Goldust still left with the title after Aksana distracted DiBiase long enough for Goldust to hit his finisher on him. Goldust and Aksana were married on the November 2 episode of NXT with father Dusty Rhodes and real-life half-brother "Dashing" Cody Rhodes in attendance. Immediately afterwards Aksana slapped Goldust and walked out on him. The following Monday on Raw Aksana stole the Million Dollar Championship belt during Goldust's match with Ted DiBiase. The following week on Raw Goldust managed to steal the Million Dollar Championship belt back from Aksana and then returned it to Ted DiBiase, Sr. and, on NXT he asked Aksana for a divorce after she was eliminated.

On December 7, 2010, it was reported that Goldust had suffered a shoulder injury. He underwent surgery to repair the injury on December 10 and, as a result, was expected to be out of action for five to six months. On the April 11, 2011 episode of Raw, he was seen (without makeup) hugging Edge after his retirement speech. On July 11, Rhodes began working backstage as a producer. On November 29 episode of Smackdown Live Holiday Special Goldust made his surprise return on a backstage segment with his father Dusty Rhodes. On December 12 episode of WWE Slammy Awards he appeared to announce the Slammy for A-Lister of The Year with Vickie Guerrero. On the December 30, 2011 episode of SmackDown Rhodes appeared in his suit attire and no make up, to defend Booker T and confront his half brother, Cody Rhodes. Rhodes made an appearance on the April 9, 2012 edition of WWE Raw, he, along with numerous other WWE officials and superstars, were attempting to break up a brawl between Brock Lesnar and John Cena. On May 6, 2012, WWE acknowledged Goldust's departure from the company.

He returned to WWE as Goldust as the eighth participant in the Royal Rumble on January 27 but was eliminated by his brother Cody Rhodes. Although he hinted at a possible feud with his brother and appeared on an episode of the JBL and Cole YouTube show, he later confirmed in an interview that his return was a one night only deal. After Cody was storyline fired in September, Goldust returned to face WWE Champion Randy Orton in a non-title match to get his brother rehired on the September 9 episode of Raw, but was defeated. On the 23 September episode of RAW, Goldust and Cody Rhodes rushed out of the stands to briefly ambush the Shield before their 11 on 3 Handicap match-causing them to get thrown out of the building. Later, he got involved in Rhodes Family vs. McMahon Family feud alongside with his father, Dusty and Cody. At the WWE Battleground PPV, Cody and Goldust defeated Roman Reigns and Seth Rollins of the Shield, thus earning Cody's job back and reinstating Goldust to the WWE roster as well. The following night on Monday Night Raw he teamed with Cody Rhodes and Daniel Bryan to defeat The Shield via disqualification. On October 11 edition of SmackDown he teamed with Cody Rhodes to defeat Erick Rowan and Luke Harper representing The Wyatt Family and giving Eric Rowan and Luke Harper their first loss as a tag team.

On the October 14 episode of Raw, Goldust and Cody defeated Rollins and Reigns in a No DQ match to win the WWE Tag Team Championship, thus marking Goldust's first title in WWE in nearly 11 years. At Hell in a Cell, the Rhodes brothers' first successful title defense came with winning a triple threat match against the Usos and Rollins and Reigns. At Survivor Series, Goldust alongside his half-brother Cody, participated in the traditional Survivor Series Tag Team match where Goldust survived till the final two alongside Rey Mysterio. However, he got eliminated by Roman Reigns and his team lost, too. At TLC: Tables, Ladders & Chairs, the Rhodes Brothers made a successful title defense in a fatal-4-way elimination match against Curtis Axel and Ryback, the Real Americans and Big Show and Rey Mysterio. But they lost the titles to Road Dogg and Billy Gunn at the Royal Rumble. Later in the Royal Rumble match, he would accidentally eliminate Cody Rhodes.After continuing to team together for months, Goldust and Cody broke up in June, after amounting losses. Cody prompted Goldust to find a new partner to replace Cody Rhodes. On Raw the next night Goldust teamed with Sin Cara but lost to Ryback and Curtis Axel, the next week on Raw the same happened with R-Truth.

On the June 16 episode of Raw, Cody debuted a new character, Stardust, wearing facepaint and a bodysuit and adopting mannerisms similar to those of Goldust. With Rhodes under a new gimmick, he teamed with his brother to quickly defeat Rybaxel by way of an improvised pin by Stardust.

On the August 25 episode of Raw, Goldust and Stardust defeated The Usos in a title match via count-out, but, as a result, they did not win the title. Goldust and Stardust would then attack the Usos out of frustration, turning heel in the process. The duo confirmed their turn heel after attacking El Torito the following night on Main Event, having defeated Los Matadores in their tag team match. On September 21 at Night of Champions, Goldust & his brother Stardust defeated The Usos to become the WWE Tag Team Champions. At Hell in Cell they retained their title one more time by beating The Usos . They lost the titles at Survivor Series to The Miz and Damien Sandow.

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