2. Rey Mysterio & Batista
Following Eddie Guerrero's tragic death, Rey Mysterio formed a bond with the then-World Heavyweight Champion Batista. The two men both loved Eddie and wanted to honor him. They did just that a month after his death by defeating MNM and winning the WWE Tag Team Championships.
The duo lost their titles two weeks later to MNM but remained friends for years. They eventually got another shot at the gold in 2009 when they faced Jeri-Show at Hell In A Cell. Batista and Rey came up short and eventually split when The Animal destroyed his former friend.
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1. Rey Mysterio & Eddie Guerrero
Eddie Guerrero is a central figure in the life and career of Mysterio. The two all-time greats formed a friendship during their early years in the industry from their mutual backgrounds from legendary Mexican wrestling families. Their friendship transformed into a brotherhood as they grew together in ECW and WCW.
Their classic matches in the latter put their names on the map. In WWE, their interactions were limited to tag teams and multi-man matches early on. Rey and Eddie first formed a tag team for the company in 2005 when they defeated The Basham Brothers to win the WWE Tag Team Championships. However, this seemed like it was part of a bigger story.
The two superstars became the first WWE Tag Team Champions to face each other at WrestleMania. Rey beat Eddie and this started a slow, steady breakdown for Guerrero. This crack in their team led to MNM defeating the duo to win the gold.
A loss in a rematch was followed by Eddie betraying Rey and ending their partnership. For pure chemistry, this is easily the best tag team that Mysterio has ever been a part of. That's why Eddie Guerrero is the biggest WWE superstar that Rey Mysterio has teamed up with.