Heterojunction engineering is regarded as one of the most efficacious means to enhance the hydrogen evolution performance of photocatalysts. In this research, bimetal MOF‐74 is grown on hollow Cu 7 S 4 , and after vulcanization, H‐CuS/NiS 2 @CuS is obtained to form heterostructures. The experimental results indicate that the synthesized H‐CuS/NiS 2 @CuS has an outstanding photocatalytic hydrogen evolution rate of 17.66 mmol g −1 h −1 , and its photocatalytic hydrogen evolution performance is much higher than that of single transition metal sulfide. Within the S‐scheme heterojunction, the interfacial electric field causes a significant accumulation of photoelectrons on the conduction band of NiS 2 . Thus, it can maintain a high reducing property in the hydrogen evolution reaction and remarkably boosts the separation efficiency of photoelectrons and holes. This research offers a feasible scheme for the synthesis of highly efficient heterojunction photocatalysts.