I don't have too much of an experience on the PS3 as I came into it super late (about half a year before PS4's release) but I have played enough to make a list for myself, so here we go:
5) Sonic Generations: As a sonic fan since SA1, this was one of the best sonic titles I've played in a long time. The speed is great, the platforming is fun, and the levels are awesome to replay, The only thing that I didn't like about this game was the final boss and the themes of the levels (which were fan chosen I believe).
4) Rayman Legends: This. This is a platformer done right. The levels are fun, the game is not cheap, the story is simple for a platformer, and the multiplayer led to great times. You don't even need much experience of Rayman to enjoy this game.
3)Borderlands 2: I am not much into shooters or RPGs, but this one captured my interest and held it throughout the game. Mostly due to the story and comedy the game provides (butt-stallion and bonerfarts come to mind) the abilities system was fun, and finding new weapons was satisfying when better than my current weapons. My only problems with this game was multiplayer when I wasn't hosting (probably on my end though) and grinding for level ups when going from story mission to story mission.
2) Saints Row: The Third: this was one game I had an awesome experience with. The story was interestingly weird, the gameplay was fun, and it was hilarious overall. This was also my first real open-world game not counting sampling GTA 3 at a cousin's house. Best part about this game: running around as a sentient toilet with an octopus bazooka hypnotizing people to do my bidding. Not joking.
1) Hatsune Miku Project DIVA F: Seeing as I love rhythm games, this game goes on the top of the list. the song list was amazing for me (impressive since I went into this blind), the graphics are great for late PS3, the gameplay was addicting, and the other modes are decent enough to warrant time to put it for me. The edit mode is also keeping me glued to the game at the moment, now that I figured out how to use it effectively. The game's only problem is that you are forced to play normal to unlock hard, and repeat to unlock expert.
This list is only current as I am still buying games for this system and it might be a long time before I jump on the PS4 bandwagon. I do plan on getting games such as No More Heroes Paradise, the Batman Arkham games (maybe skip on Origins from what I'm hearing), the LBP games, and many others. I would like to hear what others would recommend though.