The wars winners enforce it on the losers at the conclusion of hostilities.
If both belligerents are relatively weak, a more powerful third party may enter the conflict under the pretense of enforcing Geneva conventions – like the Balkan wars in the 1990s.
A powerful nation only follows them as necessary to placate their allies. There is no enforcement, nor is any nation realistically capable of enforcing it against a superpower.
Armies do have *some* incentive to behave, so that their own prisoners are treated well in kind and enemy soldiers and civilians are less likely to fight to the bitter end. You get a lot less last-stand heroics and kamikaze bombers if they think they’re free to surrender.
There are also semi-formal agreements to avoid certain tactics so that they’re not used against you – Hitler was personally injured by a poison gas attack in WWI and had a tacit agreement with allied forces during WWII to not deploy them.
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