My favourite companions are Lae'zel, Karalach, Wyll and Jaheira. Lae has just such a great story and Karlach and Wyll are great together and I love their Avernus ending. Jaheira is just her awesome self, I always liked her in the other games and Larian really did her justice.
NPCs I really like are
Barcus, he is just the best.
Korrilla and Hope Hearthflame - I really wish,we could have explored their tragic and messed up backstory more.
Florrick - love her, sadly, she has not enough screen time
Abdirak - I really liked, how wholesome he was for a priest of an evil goddess. And I'm sad, they didn't do more with him in act 3, especially, since there is the whole story with the Ilmater temple and Loviatans and Ilmaterians don't really get along. Plus Loviatar is loyal to Bane, which could have made for a whole new dynamic all together.
Rolan and his siblings, Zevlor and Dammon from the tieflings, I just like them
Arabella - she is awesome and I love her interactions with Withers
Dame Aylin - she is a lot, but I love her
Enemies, I really like
Auntie Ethel - she is so much fun and so well done.
Raphael - probably the most fleshed out of your ( potential, since you can just sign the contract) enemies. He is tons of fun too and the House of Hope probably my favourite map. The voice actor does a really great job.
Ketheric - good build up, tragic story, great voice actor, what's not to like
I would put Gortash on the list too, since in theory, he is great as a character and adversary, but he just comes in so late and you learn most of his shenanigans through letters and diaries and I would have preferred more direct interactions, maybe some political intrigues.