Simultaneous　utilization　of　photogenerated　electrons　and　holes　within　a　photoredox　system　enables　effective　hydrogen　(H2)　production　and　organic　synthesis,　aligning　with　eco-friendly　chemistry　principles　and　current　energy　challenges.　Here,　we　report　the　preparation　and　application　of　cocatalyst　MoS2　decorated　CdS　(MoS2[sbnd]CdS)　composites　for　the　photoredox-mediated　C–N　coupling　of　amines　to　imines　and　H2　generation　under　visible　light　illumination.　The　H2　and　N-benzylidenebenzylamine　yields　for　the　optimal　MoS2[sbnd]CdS　are　28.9　and　15.0　times　higher　than　those　of　bare　CdS,　respectively.　Mechanism　studies　reveal　that　the　enhanced　photocatalytic　activity　results　from　the　MoS2　acting　as　an　electron　sink,　which　accelerates　the　separation　and　migration　of　photogenerated　charge　carriers.　Additionally,　the　pH(•CH)NH2　intermediates　are　found　to　play　a　pivotal　role　in　the　dehydrogenative　coupling　of　benzylamine.　Furthermore,　the　MoS2[sbnd]CdS　composites　exhibit　universal　applicability　in　the　conversion　of　various　aromatic　amines　into　corresponding　imines　integrated　with　H2　evolution.　©　2024　Elsevier　B.V.