Probably ToV (Tales of Vesperia), with over 90+ hours, TotA (Tales of the Abyss) with around 60hrs. Mirror's Edge, maybe around 20hrs. Project Diva (That Vocaloid game, yes LOL.) with around 10 hours..
As for mmo's..Flyff would probably be it. Private servers and real servers. 100 hrs I believe. That's a long time to stick with a ftp mmo, in my opinion. Maple Story with Pservers is prolly 50hrs. (the real server is shit, if you ask me.)