1. Montgomery Burns
As Homer Simpson's tyrannical multi-billionaire boss, "Mr." C. Montgomery Burns espouses all the characteristics of a supervillain – many of which owe a huge debt to Harry Shearer. From the diabolical way he seems to hum the word "excellent!" whenever he implements an evil plan to the befuddled way he forgets Homer's name like it's Homer's fault, Shearer's ability to get inside the bald head of Mr. Burns (and all his myriad look-alikes) has been a part of what has made The Simpsons great. Most chilling: the disarmingly saccharine manner in which Shearer's Mr. Burns answers the phone, "Ahoy-hoy?"