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If you attempt to connect a previously used controller with a new PS3, they will not pair properly until the old stored information is cleared. Pairing problems can also occur even if you have been using the same controller and console together for some time. Firmware updates or loss of power can also disrupt pairing.
Reset Pairing
Turn your PS3 console on as usual. Use the USB cable supplied with the Sixaxis to connect the controller to one of the ports on the front of the console. The console will automatically begin clearing old pair data and replacing it with the data to be used for the new console/controller pairing.
Setting a Controller Number
Wait a few seconds for the sync to complete. The console will then automatically assign paired controllers with a number in the order that their connections are recognized. The Sixaxis will display its assigned number by turning on a small light next to one of the numbers at the top of the controller. Though there are only four lights, the PS3 can simultaneously pair with up to seven controllers. If your controller is assigned to a number greater than four, it will turn on two lights that add to its number.
Wireless Controlling
As long as a controller's battery is charged, you can remove the USB cable and use the controller wirelessly at any time. There is no need to turn the console off before connecting or disconnecting a USB cable. You can check a controller's battery level at any time by pressing the "PS" button in the center of the controller.