NiS　is　deposited　on　the　surface　of　hexagonal　ZnIn2S4　via　a　hydrothermal　method　and　the　as-obtained　NiS/ZnIn2S4　nanocomposite　shows　superior　activity　for　photocatalytic　dehydrogenative　coupling　of　amines　to　produce　imines,　with　simultaneous　generation　of　hydrogen　under　visible　light.　The　superior　performance　over　NiS/ZnIn2S4　for　photocatalytic　dehydrogenative　coupling　of　benzylamine　to　produce　N-benzylidenebenzylamine　can　not　only　be　ascribed　to　NiS,　which　acts　as　a　cocatalyst　to　promote　the　charge　transfer　and　hydrogen　evolution,　but　also　attributed　to　its　strong　adsorption　toward　benzylamine　and　its　relatively　weak　adsorption　toward　the　product,　which　is　also　proved　by　density　functional　theory　calculations.　This　study　not　only　provides　an　efficient,　green,　and　cost-effective　strategy　to　produce　imines,　but　also　demonstrates　that　the　adsorption　of　the　photocatalyst　toward　the　reactants　and　the　products　is　an　important　issue　that　should　be　considered　in　a　photocatalytic　reaction.　©　2022　Wiley-VCH　GmbH.