Coupling　hydrogen　fuel　production　with　selective　oxidative　organic　synthesis　in　one　cooperative　manner　offers　a　promising　avenue　to　enable　efficient　utilization　of　photoexcited　carriers　to　achieve　sustainable　chemistry.　Herein,　a　new　Mo2N/Mn0.3Cd0.7S/CoPi　photocatalyst　is　reported　for　visible-light-driven　hydrogen　production　paired　with　selectively　oxidative　C[sbnd]C　bond　formation.　Mo2N　acting　as　electron　collectors　and　reduction　sites　are　adsorbed　on　the　Mn0.3Cd0.7S　by　interfacial　Mo-S　bond,　while　CoPi　acting　as　hole　collectors　and　active　sites　for　oxidation　reaction　are　deposited　on　Mo2N/Mn0.3Cd0.7S.　Remarkably,　the　synergetic　effect　of　Mo2N　and　CoPi　dual　cocatalysts　results　in　the　adjustable　flexibility　of　switching　benzaldehyde　(BAD)　production　to　C[sbnd]C　coupling　synthesis,　thus　exhibiting　the　high　selectivity　of　C[sbnd]C　coupling　products.　Mechanism　studies　indicate　that　the　C[sbnd]C　coupling　reaction　occurs　through　a　free　radical　mechanism.　The　present　work　gives　insight　for　achieving　highly　efficient　C−C　coupling　synthesis　with　hydrogen　evolution　by　loading　dual　cocatalysts.　©　2021　Elsevier　B.V.