Click on their username, a pop up box appears, then click where it says "add to friends list". This sends them a friend request they can accept or decline in live chess. Is that what you meant ?
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I would like an "Add as friend" button in live chess. Occasionally, I meet someone cool over there, and would like to play them again. Of course, I never remember to exit live chess, go to my home, and send a friend invite.