It should sinc if you push the PS button, but if not you can plug the controller into the playstation with the charger and then try again
If the controller is being connected for the for the first time and is not an official Sony ps3 controller and it is a ps3 compatible controller, connect the controller with a USB cable to the ps3, then under settings> device settings> register new device. This is how it works for Wired and Wireless headsets for the ps3 too.This sectional guide answer was modified by TechnoFixunder 'Modified for a wider understanding'.
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To connect any controller to a PS3 first plug in a USB cable to the controller. Connect this cable to the PS3 you want to connect the controller to. Press the PS button and the controller will connect.
The PS3 Dual Shock 3 controller is a Bluray controller for the PS3 exclusively
You use the charging cable to connect the PS3 to Controller and press the Playstation Emblem on the controller
turn on a ps3 then turn on a controller, any ps3, any controller.
When the PS3 is on use the charging cable to connect the controller to the PS3 and press the Playstation Emblem on the controller