Photochemical　dehydrogenation　of　N-heterocyclic　amines　to　corresponding　N-heteroaromatics　paired　with　hydrogen　(H2)　production　represents　a　promising　route　for　the　green　and　sustainable　organic　synthesis　and　clean　fuel　generation.　Herein,　metal-organic　frameworks　(MOFs)-supported　CdS　nanoparticles　are　gingerly　fabricated　for　the　visible　light-initiated　acceptorless　dehydrogenation　of　diverse　N-heterocycles　at　ambient　conditions.　With　further　nickel　cocatalysts　modification　via　a　simple　photodeposition　method,　the　optimized　MIL-101　@CdS-Ni　composite　exhibits　remarkably　enhanced　activities,　which　are　8　folds　higher　than　that　of　binary　MIL-101　@CdS　and　2.8　times　higher　than　that　of　MOF-removed　CdS-Ni　counterparts,　along　with　high　selectivity　and　good　stability.　Mechanism　studies　reveal　that　active　nickel　species　plays　a　key　role　in　accelerating　the　separation　of　photogenerated　charge　carries　and　the　cleavage　of　C−H　and　N−H　bonds　in　the　scaffold　of　N-heterocycles　on　the　catalyst　surface.　This　work　is　expected　to　guide　the　rational　catalysts　design　of　MOF-based　multifunctional　materials　for　photochemical　coupling　of　concurrent　organic　synthesis　with　H2　production.　©　2022　Elsevier　B.V.