High-quality　interfacial　coupling　can　effectively　boost　photogenerated　charge　separation/transfer　efficiency.　Herein,　we　develop　a　multicomponent　photocatalyst,　Co6Mo6C2-MoO2-CoNC@ZnIn2S4　(CMN@Z),　featuring　directional　and　swift　carrier　transfer　ability　through　interfacial　microenvironment　modulation.　The　distinctive　CMN@Z　displays　a　ten-times　enhanced　photocatalytic　H2-production　performance　of　4728　μmol·g−1·h−1　than　pure　ZIS,　accompanied　by　optimized　apparent　quantum　efficiency　of　25.06　%　at　420　nm.　Typically,　the　well-tuned　Schottky　barrier　readily　balances　its　bifunctionality　in　rectifying　effect　and　powerful　photogenerated　electron　extraction　impetus.　Moreover,　the　gradient　work　function　variation　enables　the　interfacial　potential　as　a　robust　driving　force　to　expedite　charge　transfer.　Therefore,　the　resulting　cascade　charge　channel　and　intimate　interfacial　contact　endow　CMN@Z　photocatalyst　with　optimized　H2-production　performance　by　virtue　of　high-efficiency　carrier　spatial　separation　and　utilization.　Our　work　deeply　explores　the　role　of　multiple　interfacial　in　coupling　photocatalytic　systems,　which　offers　new　insight　into　the　rational　design　of　cascade　photocatalysts.　©　2022　Elsevier　B.V.