Mmm, it's hard for me to chose since I watch a bulk of it multiple times, so for me I'd have to lump it into 3 different categories: Movies, English, and Japanese. As far as the Japanese goes I have most of it, except for Thriller Bark, a lot of Enis Lobby and the second half of Skypiea (yeah, the good part ><), so I end up watching the first half of Skypiea a lot–especially Jaya. I also like the Rain Dinners eps. of Alabasta, and the last eps of Alabasta with the feast and Bon Clay, also Vivi's speech. Also watch a lot of Water 7 (which I'm also missing a chunk of right after Franky's second flashback episode, boo), and the end half of Enis Lobby/Water 7, especially the last few episodes with Franky joining and the crew departing/Usopp returning.
As for movies, I only have 4 of them (have seen all except the first one), and I know the one I watch the most is Movie 6, with Movie 4 coming in a close second (only because I felt the ending was a little weak). With the English I have the entire first season --the last two of which were gifts, because I am poor ;__;, and out of that I like watching Usopp's arc and the end half of Arlong Park. I know once I get my S2V3 dvd (which I ordered but is late getting here, boo) I'll probably watch that a lot too, because I love Chopper's english VA (Vivi's too, and this is the first english I'm getting with her other than movie 8)..and I did watch Drum Island a lot in Japanese as well.
EDIT: Ack, almost forgot, I also watch Brook's 2 flashbacks episodes a LOT, especially the first one, because lil' Laboon is waaaay too cute ^^ Also watched it alot so I could memorize Binks Sake, lol.