1. The Borg. 
Fixed =)
My own list:
Darth Sidious (Star Wars)
Anti-Spirals (Gurren Lagann)
The Demiurge (Kult PnPRPG)
Kefka (FFVI)
Victor von Doom, aka Dr Doom (Marvel Comics)
Ganon (Zelda)
Kane (C & C)
Walter o'Dim/The Man in Black/Randall Flagg (several Stephen King novels)
Gollum (LotR)
I'm not going to number them, since I don't know which one I prefer. I will, however, motivate my choices.
Doom, Ganon, Kane and Walter are all tenacious villains. Once defeated, they come back, again and again. Defeat is always "just a minor setback" on their way to total world domination/godhood or whatever. Doom makes it into this category not by being immortal or timeless like the other three, but by sheer willpower and stubbornness, which is a great merit in itself.
The anti-spirals and the demiurge make the list together for doing something so grand as to remove a whole race from godhood (or god-like status) to "protect the universe". Both have constructed extremely elaborate systems to keep mankind in place, and elaborate systems are part of what makes a good villain.
Kefka is an evil, insane clown who aspires to godhood and succeeds in grasping it and reshapes the world as he sees fit. You don't get more villainous than that.
Sidious makes the list for being a brilliant schemer, twisting an entire galaxy to his will. That and being the best in the world at saying "Goooooood".
Gollum makes it here for being the most complex villain in the LotR books as well as the world's most awesome junkie.
Comments on other's lists:
I don't think Sauron (post Silmarillion) is a very interesting villain. As he appears in the LotR trilogy, he's almost not even a proper character, but much more like a backdrop to create other villains from.
I don't really see the Borg as villains, really (I deny the existence of the Borg Queen, she's just silly). They are more like a force of nature, akin to the Nothing in the Neverending Story.