I’m…assuming that, for the situation the OP’s thinking of, whatever villainess isn’t just going to murder me afterwards (or during)? Cause…y’know…that’d just ruin the whole experience for me in advance. But maybe that’s just me.
But yeah, Baroness, Mystique, Shego…they’re the ones who come to mind for me, too, but I should probably still add someone else.
The trouble with villainesses is that you have to liquidate them so early into a love affair that you really end up having a series of meaningless flings, and that takes a villains mind off the business at hand. Nonetheless, I’ve always been fond of Alotta Fagina, who was feathured in an excellent 1997 spy documentary.
I can’t find anything on imdb, but I distinctly remember one of the Power Ranger clones that was playing in Japan around '96 or '97, the woman playing the queen of the monsters was either currently working in or had just left hardcore porn (one of the female rangers had also just released a book of nude photos, so overall it was a fun show). I also recall her costumes on the show weren’t much less revealing than her film outfits. So there’s a VILF that I’ve seen F’ing.
The beauty of the VILF concept is the lack of potential for a long term relationship, but of course self preservation can be a problem. My choice is Lilah Morgan from Angel but I may think of others later.
The Boss from Metal Gear Solid 3. All the other villainesses in video games seem too stereotypically “hot” for me, but this character actually seemed like a rugged, take-no-shit woman who also had a haunting sense of loneliness about her - a really well-developed character all around, with a great voice also.