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Found a song I like... guess I'm an animatic/lyric video maker now
(reylo reincarnation au)
WIP
BONUS: Rune Factory 4
M/F
Stretches the definition slightly, but 4 of the marriageable characters are boss monsters you have to defeat before you can befriend/date them (2 M, 2 F)
One of the LIs is also a spy/traitor. There's no big bad villain LI though.
BONUS: Avalon Code
M/F
An RPG for the DS, where you can play as a boy or girl. It has a subplot where you can build romantic relationships. (strictly het, unfortunately). One of the potential LIs is Prince Valdo, who serves as the big bad for most of the game.
Memoirs of an Angel
M/F
This one was pretty big in the early 2010s OELVN scene (alongside RE: Alistair, Planets and Frozen Essence). Haven't played it personally but it seems to have a villain LI.
Soulset
M/F
This game has both M/F and F/F routes, but the (secret) route I'd consider the "antagonist" route is M/F. Less outright villainy and more behind the scenes machinations and masterminding.
Hakuoki
M/F
Hakuoki is the skyrim of otome games, with its 100000 ports and spinoffs. One bad guy/antihero route.
Seduce Me 1 & 2
F/F, F/M
This one's pretty infamous. The protagonist starts living in a house with a bunch of incubi. Many M/F routes but one antagonist M/F and F/F routes respectively.
Norn 9
M/F
Also haven't played, but I have heard about one of the LIs being an antagonist.
Mystic Messenger
M/F
MC is trapped in a death-game amusement park. Secret villain route!
Period Cube
M/F
Secret villain route. The writing quality of this game is... hotly debated among otome circles.