http://forums.steampowered.com/forums/showthread.php?t=1319656
Andyman 64 says I can. Does it depend on the game?
If you read anyman614's post, he says you can use the Steam overlay to chat with friends via Steam - that is different then joining their games via Steam, which requires the game to be distributed through Steam / Steamworks.
Basically you can chat with friends via Steam in a non-Steam game (such as a disc copy of Oblivion) but you cannot invite friends to join you - or join their games via Steam - in said retail game's multiplayer unless that game is sold through Steam.