How to remove PSN account from PS3
You can remove a PSN account from your PS3 by going to 'Settings' > 'System Settings' > 'Delete User'. Just pick the user profile you want to remove.
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Honestly, if it's just one account, creating a new user profile on your PS3 might be faster and simpler.
Personal experience: Go to 'Users' on the far left of the XMB, highlight the user you want to delete, press △, then select 'Delete'. Works every time!
Go to 'Settings' > 'Account Management' > 'System Activation'. Deactivate your PS3 from there, then delete the user profile associated with the PSN account. Easy-peasy!
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