For Me:

Kwon Jae-hee (played by Nam Gung Min) from The Girl Who Sees Smells

Nam Gyu-man (played by Nam Gung Min) from Remember: War of the Son

Chae Do Woo (Kim Kang Woo) from A Man's Story
Gwi (Lee Soo Hyuk) from Scholar Who Walks the Night
Gi Cheol (Yoo Oh Sung) from Faith
Cha Do Hwi (Park Soo Jin) from Flower Boy Next Door
Min Joon Kook (Jung Woong In) I Hear Your Voice
I agree re: My Love from the Star villain. He is so hilariously evil, he just needs a mustache he can twirl. 

The mums from Pinocchio - it's such a cliche in kdramaland, but parents do make good villains I have to admit 
+1 Min Joon Kook (Jung Woong In) I Hear Your Voice
Jang Hyun Sung - signal (i hated him the whole time)
Song Yoon Ah - the k2 (fav female villian, a extreme manipulative character)
Jang Mi Kwan - Strong Woman Do Bong Soon (loved his portrayal.......just wished it was done in a crime triller than rom-com kinda series)

from the my current completed list
Song Yoon ah from K2 was perharps the best villian i have ever watched in a kdrama. She was not evil, and her motives made sense. I could sympathise with her and in the scene when she tells yoona that she has the capacity to become like her, I was just like wow, she made perfect sense because yoona was ridiculously similar to her in circumstance. Her acting also sold me. Song Yoon Ah is one of my fav actress
Min Joon Kook - I Hear Your Voice +2
David Agus - Descendants of the Sun
Jang Hyun - Strong Woman Do Bong Soon
Cha Minho from Defendant and Ji Se Gwang from Incarnation of Money.
For me it's Wang Yo-Scarlet Heart Ryeo.....I hated him,but towardthe end I felt so sorry for him:/ 
Lee Jae Kyung - My love from the star
Kwon Jae-hee -The Girl Who Sees Smells
Tae Ho - Missing 9
Shin Tae Hwan - East of Eden
Shin sung rok of You Who Came from the Star and Liar Game

Nam Goong Min - Remember: War of Son
Jung Woong In - I Hear Your Voice
Shin Sung Rok - You Who Came from the Stars
Mishil - Queen Seon Deok!!! I loved her so much. Probably my favorite villain ever. 
Ki Cheol - Faith. This is a villain that I really appreciated the first time I watched but not as much the second time. idk I liked that he was vulnerable and we really got to see him struggle (not because of the main characters, but because of his own worries. It made him more like a character than just a villain whose only purpose is to make a plot.). I just appreciated that he had a purpose behind his motives I guess.