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A Bluetooth headset has to be registered, or "paired", with your PS3 before it can be used.
Make sure your Bluetooth headset is fully charged before you begin.
Check your headset instructions for entering "pairing mode". Activate your headsets' "pairing mode" so it can be recognized by the PS3.
On the Cross Media Bar (or XMB) of the PS3 go to the "Settings" tab, then down into "Accessory Settings", then down into "Manage Bluetooth Devices".
With your headset in pairing mode, follow the onscreen instructions and let the PS3 scan for your headset. When your headset is found, follow the prompts and enter a pass key (if necessary- the default is usually 0000 for all brands). The pairing should now be complete.