Abstract <p>Designing photocatalysts with suppressing recombination of photogenerated carriers that simultaneously deliver high efficiency and long-term stability, remains a key challenge in hydrogen evolution. Herein, a hybrid photocatalyst comprising g-C₃N₄ coupled with a minimal amount of nanoscale bimetallic CoFe-MOF is presented, where the MOF serves as a charge-regulating and stability-enhancing component. Mott–Schottky and photochemical analyses unveil the formation of an interfacial heterojunction between CoFe-MOF and g-C₃N₄, which promotes efficient charge separation and directional charge transfer across the interface. The optimized CoFe-MOF/CN hybrid exhibits a high hydrogen evolution rate of 11.7 mmol g^–1 h^–1 under visible-light irradiation, ranking among the highest reported values for MOF/g-C₃N₄-based photocatalysts. The enhanced photocatalytic activity stems from the integration of the bimetallic CoFe-MOF, where the synergistic Co²⁺/Co³⁺ and Fe²⁺/Fe³⁺ redox centers facilitate efficient charge transfer, while the nanoscale morphology ensures optimal interfacial contact and high utilization of active sites. Furthermore, the hybrid demonstrates excellent durability over seven consecutive cycles and a maximum apparent quantum yield at 420 nm, confirming efficient visible-light utilization. This work showcases a rational approach for achieving a balance between high efficiency and long-term stability through function-oriented MOF integration, providing new insights for designing heterojunction photocatalysts for hydrogen evolution.</p> Graphical abstract <p>Under light irradiation, the Type-I heterojunction formed between g-C₂N₄ and CoFe-MOF enables the simultaneous migration of photogenerated electrons and holes from g-C₂N₄ to CoFe-MOF, promoting charge accumulation on CoFe-MOF and facilitating the proton reduction to H₂ in the presence of TEOA.</p>