I fell in love with Hisoka's character during the HxH Hunter test, when he brings back Leorio from the fog forest instead of either outright killing him or leaving him behind.
And Kuki Hideo from Majikoi, after he gets rejected. Guy just grew on me.
In any case, this thread made me realize how few female characters in anime/manga/VNs are either 1) likeable as a character or 2) likeable as a person. Yosomiya Tsuzuriko from Kara no Shoujo and youkai mom from Erased would be 1s, while I've-also-masturbated-to-you-before from Kokoro Connect and the grandma from GATE would be 2s. Outside of those four, I'm struggling to think of any likeable girls or women.