I'm talking flat out villains..for example, The Punisher is NOT a villain, but Darth Vader is, in his Sith form, not as Jedi Anakin.
As a mostly Villain fan, I will list mine but am not sure if I can pick a #1 at this point:
-Storm Shadow Cobra villain from the comics (the brutal, unstoppable killing machine that worked for Cobra, pre-face turn to GI Joe. Not the movie or good guy versions)
-Darth Maul (The consumate Sith, Bushido Warrior)
-Cobra Commander (The logical, strong version from the "Cobra Reborn" comic series and not the bungling, scared, weak versions portrayed elsewhere)
-Heath Ledger's Joker (The most amazing actor portrayal of a true homicidal comic villain. Pure genius.)
-Galvatron (Crazed, unstoppable, ruthless Leader of the Decepticons)
-The Hobgoblin (The Marvel Comics version, thought to be Ned Leeds then discovered to be Roderick Kingsley)
-Apocalypse (The first Mutant, the Alpha and Omega, The Leader of The Four Horsemen)
-Nature Boy Ric Flair (Pro Wrestling's greatest heel and leader of the classic Heel Team The Four Horsemen, personified the vision of what a true villain should be in the wrestling world)
-Hush (My favorite Batman villain, yet I do not acknowledge the "Heart of Hush" storyline)
-Neil McCauley from "Heat" as portrayed by Robert DeNiro (youtube the character and see for yourself)
I'm sure there are several that I have forgotten, but the fact these each of these come to mind immediately makes them special in mind.
Anyone else?