Based on the structural characteristics of bimetallic phosphates, the rod‐like NiCoP/NiMoO4 heterojunction composite catalyst is successfully synthesized by hydrothermal method, which realizes the rapid transfer of photogenerated carriers across the heterojunction interface, thereby improving the performance of photocatalytic decomposition of water to produce hydrogen. Through photocatalytic experiments, the hydrogen evolution rate of the NiCoP/NiMoO4 is 61.4 μmol h−1, which is 2.93 times that of pure NiMoO4. Further study on the catalyst shows that this structure could greatly improve the utilization rate of sensitizer and hole sacrifice agent in the dye sensitization system, and the rate of photon‐generated carrier separation and transfer is significantly improved to achieve a good hydrogen evolution effect.