#1 Eddie Guerrero
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At No Way Out 2004, Eddie Guerrero took on Brock Lesnar with the WWE title on the line, going into the match as the ultimate underdog. He had won the 15-Man "SmackDown Royal Rumble" to earn the opportunity.
Guerrero ended up defeating Lesnar in one of the biggest upsets in WWE history, after some assistance from Goldberg. He went on to successfully defend the title against Kurt Angle at WrestleMania 20. Around two years before they collided, Lesnar and Eddie once teamed up on an episode of RAW, in June 2002.
Eddie defeats Lesnar:
This was when Lesnar had recently made his WWE debut, and Eddie was a heel. Lesnar and Eddie took on two fan favorites in Bubba Ray Dudley and Rob Van Dam. The villains stood tall when the match came to an end. Lesnar would go on to defeat RVD in the King of the Ring finals to bag an opportunity at the WWE title at SummerSlam, where he would put down The Rock to become the youngest WWE Champion.