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.