Photocatalytic　hydrogen　(H-2)　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　H-2　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　H-2　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　H-2　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.　(C)　2021　Elsevier　Inc.　All　rights　reserved.