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A Song of Ice and Fire by George RR Martin ^
There is A LOT of villain romance here but I WILL TAKE THE TIME TO HI LIGHT this romance between a guy who threw a child out of a tower and a strong beefy pure kind lady knight who really wants to bone him.
And I Darken by Kiersten White
The main character is a villain and shes also thirsty for her childhood friend who is also her enemy who is also the primary love interest of her brother so. Take that how you want.
the Kushiel series by Jacqueline Carey*
Very intense super sexual UST serious chemistry between the main character and the big bad (F/F)
The Invisible Life of Addie LaRue by VE Schwab ^
Potential romance between basically the devil and a lady he granted immortality to and now has been harassing for centuries.
The Daevabad series by S. A. Chakraborty *
Romance is between a thief with a heart of gold and her monster boyfriend and bodyguard who is a very old legendary murder of thousands.
I made this SPN graphic in 2014 and people still reblog it all of the time.