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She was a pretty sympathetic villain, though. She just want about it all wrong.
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She was a three dimensional villain, which is why she tops my list.
Plus in the villager's flashback halfway through I could totally imagine the Imperial March playing with her walking through the flames.
If we were going for complete monsters though I'm not sure. Most of the villainous villains I know of, the ones who put the greatest show on for evil, are so past the moral event horizon that I can't find them 'cool' anymore.
A couple that do stand out, however, are Mr Croup and Mr Vandamar from Neil Gaiman's Neverwhere.