Instructions
Press the power button on the right front face of the system to turn on your PlayStation 3.
Press and hold the "PS" button in the center of your PS3 controller for approximately 3 seconds. The red light on the front face of the controller will blink and then remain on under the "1" heading. This indicates that it is the first controller connected to the system.
Scroll to the "Game" option using the controller's left analog stick and then select a game that you wish to play.
Press and hold the "PS" button on the center of a second controller for approximately 3 seconds to add functionality of that controller to the game as well. The red light will blink and then remain on under the "2" heading to indicate that it is the second player connected. You can repeat this process for up to 4 controllers total.