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Alberto Del Rio debued on SmackDown in August 2010, and immediately began a feud with fellow mexican star Rey Mysterio. The two would trade victories on television and pay per view, with both men heading their respective teams at Survivor Series in a five versus five tag team elimination match at Survivor Series 24, an exchange Mysterio would win. In the end however, Alberto Del Rio would be the winner of their feud when he finally defeated Mysterio in a Two out of Three Falls match on the January 7th, 2011 edition of SmackDown.Later that month, Del Rio would enter and win the 2011 installment of the Royal Rumble, defeating 40 other men for a world title opportunity at WrestleMania 27. He faced Edge at the event in a losing effort. Initially he was set to face Edge again at Extreme Rules in a rematch, but Edge was forced to retire due to neck injury, and the title was vacated. Del Rio instead faced Edge's real life best friend and long time tag team partner Christian at Extreme Rules in a ladder match for the title. Again, Del Rio failed to capture the gold.

WWE Champion and Various Feuds

On July 17, Del Rio won Raw's Money in the Bank ladder Del Rio as WWE Champion in 2011match to earn a contract that allowed him to face the WWE Champion at any time, at any place, within the next calendar year. He would go on to cash in his contract next month at SummerSlam 24 against CM Punkto win his first world crown one week shy of his one year anniversary of his debut. He would lose the title one month later to John Cena, only to reclaim it the next month in October at Hell in a Cell, where he defeated both Cena and CM Punk in a Triple Threat Hell in a Cell match, making him a two time WWE Champion. Once again however, he lost the title in little over a month's time to CM Punk, who has held the title ever since.In May 2012, Del Rio would once again find himself in the world title scene when he challeneged World Heavyweight Champion Sheamus along with Randy Orton and Chris Jericho in a four man match for the gold. He would lose this match, but would face Sheamus again one on one three more times at Money in the Bank, SummerSlam and Night of Champions. Each time, he failed. He then entered a feud with Randy Orton, who he would lose to at Hell in a Cell. He would lose to Orton two more times in singles competition, once in a Falls Count Anywhere Match on SmackDown, and once again in a Two Out of Three Falls match on Raw to end their feud.

Face Turn

At WWE TLC in December 2012, Alberto would come to the aid of his personal ring announcer Ricardo Rodriguez after he tried to assist the spanish announcers, who were being harassed by the Three Man Band (Heath Slater, Drew McIntyre, and Jinder Mahal.) Del Rio would then team against the 3MB with the Miz and the Brooklyn Brawler to become a face, after two years as a villain. He would cement his turn by defeating the Big Show in a Last Man Standing match for the World Heavyweight Championship on the January 8th SmackDown! tapings and retaining the gold at the Royal Rumble and the Elimination Chamber. His final successful defense came at WrestleMania 29, where he retained the championship against Jack Swagger. The next night on Raw, Del Rio would drop the gold to Dolph Ziggler, after Ziggler cashed in his Money in the Bank contract on him.

Heel Turn

Del Rio faced Dolph Ziggler for the Word Heavyweight Champioship again. However, Dolph Ziggler suffered a concussion and when Del Rio faced Ziggler after he was cleared, Del Rio targeted Ziggler's head ruthlessly throughout the match. This act turned Del Rio heel once again, but, Ziggler didn't give up and this act turned Ziggler face for the first time in his WWE career. However, Del Rio end up winning the World Heavyweight Championship where he remains currently.Del Rio then began to feud with the recently returning Rob Van Dam and lost a match against him. Furious, Del Rio viciously attacked his announcer Ricardo Rodriguez after he somewhat costed Del Rio the match. Rodriguez now works as Rob Van Dam's manager and Del Rio was managed to successfully defend the World Heavyweight Championship against RVD.