Of the ones I've played:
Grand Theft Auto IV - Hours of gameplay in single player mode.
Ratchet & Clank Future: Tools of Destruction - Good action platformer. Episodes coming to PSN.
Warhawk - Online only, but the dogfights are fun.
MotorStorm - Decent racer.
From what I have heard:
Call of Duty 4: Modern Warfare - Good FPS. Couldn't get into the PC version, so never tried PS3.
Metal Gear Solid 4: Guns of the Patriots - Heard it's good, with plenty of cutscenes.
If your PS3 is backwards compatible, you could also shop for PS2 games.
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