Instructions
Turn on your PlayStation 3.
Select the "Friends" category from the menu. Select "Start New Chat."
Select "Text Chat" if you want to have a text-based Web chat on your console. Select "Voice/Video Chat" if you want to audibly communicate with a friend over the Web. Note that "Voice/Video Chat" requires either a PlayStation Eye peripheral device or a headset microphone.
Enter a name for your chat room (for text chat). Once the room is created, go through your PlayStation Network friends list and select the friends you want to chat with. Invitations will be sent to each friend and the chat will begin when they join the chat room.
Select "Invite a Friend." Type a message to the friend and select "Send." When the friend accepts your message, you will be actively Web chatting on your PlayStation 3.