Instructions
Turn on the PlayStation 3 console to which you are syncing the controller.
Plug the USB cable that came with the PS3 into the back of the controller.
Plug the opposite end of the USB cable into the PS3 console. This will automatically sync the controller to the PS3 system.
Press the PS button in the center of the controller to assign it a controller number. Each time the PS3 system is turned on, a controller number must be assigned.
Repeat steps 2 through 4 for each additional controller you want to sync. You can sync up to seven controllers.