Photocatalytic　hydrogen　(H2)　evolution　integrated　with　selective　oxidation　to　produce　fine　chemicals　is　a　promising　strategy　for　solar　energy　conversion　and　storage;　however,　the　efficiency　of　such　coupled　photocatalytic　redox　cycles　is　greatly　limited　by　the　poor　surface　kinetics　of　hydrogen　evolution　reaction　(HER)　and/or　dehydrogenation　reaction　(DHR)　on　heterogenous　photocatalysts.　Herein,　we　demonstrate　that　the　immobilization　of　ultrafine　nickel　disulfide　(NiS2)　nanoparticles　on　CdS　nanosheets　(NiS2/CdS)　is　a　simple　yet　efficient　approach　to　kinetic　improve　the　surface　redox　reactions　for　H2　production　and　dehydrogenative　coupling　of　amines　to　imines.　The　NiS2　nanoparticles　loaded　on　CdS　not　only　function　as　the　HER　active　sites　to　speed　up　charge　separation　and　to　boost　H2　release,　but　also　enhance　the　adsorption　of　amines　to　facilitate　the　dissociation　of　C-H　and　N-H　bonds　to　form　aldimines　intermediates,　which　are　readily　coupled　with　other　amines　to　afford　a　high　selectivity　toward　imine　synthesis.　Benefiting　from　such　unique　bifunctional　catalytic　behavior　of　NiS2　in　proton　(H+)　reduction　and　substrate　activation,　NiS2/CdS　exhibits　a　remarkable　enhanced　photocatalytic　performance　toward　simultaneous　production　of　H2　and　imines.　The　apparent　quantum　efficiency　(AQE)　at　420　nm　is　calculated　to　be　54.7%.　This　strategy　using　bifunctional　cocatalysts　to　kinetic　improve　the　surface　redox　reactions　will　have　broad　implications　in　the　development　of　high-performance　photocatalysts　for　integrated　production　of　solar　hydrogen　and　value-added　solar　chemicals.　©　2021　Elsevier　Inc.