The game has to be on your steam account to buy dlc as far as i know.
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Seems this is one of the retail games that can be activated on Steam, So should answer both (but normally no steam dlc can be used on retail games, this is an exception since it's a retail game that can be activated on steam.)
https://support.steampowered.com/kb_article.php?ref=7480-WUSF-3601
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Civ V is a Steamworks game so even the retail keys tie to Steam. In which case yes he can buy G&K on Steam.
Any retail game that is Steamworks and so ties to your Steam account you can buy the DLC for it on Steam. With other retail games that do not tie to your Steam account you cannot even buy the DLC as Steam won't let you.
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I've been wondering for a while and now the issue actually has come up since I gave my boyfriend Civ V for his birthday. It's a retail physical copy though. If he bought Gods and Kings expansion on steam, would he be able to play it with his retail Civ V? (I don't know if you can redeem Civ V physical retail serials on Steam but I'd like an answer for games where you can't for an example cause it's also something I've been wondering about).
So there's basically two questions: the title which applies to all games in general (that you own a physical non-redeemable copy of), and the specific case of Civ V.
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