#1 Vince McMahon
This has to be number 1 on this list, purely for the fact that Vince McMahon was and is a non-wrestler, and made himself champion as part of the ongoing storyline with HHH and his 'kayfabe' marriage to Stephanie (which later became real life).
Vince beat HHH for the title on a SmackDown in September 1999 via outside help from Stone Cold, who wanted the title for himself. McMahon had to relinquish the title on Raw the following week without defending it, and would continue to feud with HHH up till his 'No Hold's Barred' match a few months later.
McMahon is one of the greatest heels in the wrestling business and one of the key components for the success of the Attitude Era.
Although the owner of WWE and Chairman of the Board, it was still shocking and unlikely that he considered himself to be the champion, purely due to his old school mentality and partly because, aside from being able to take bumps and provide character progression, he couldn't wrestle very well at all!