Designing functional heterojunctions to enhance photocatalytic hydrogen evolution is still a key challenge in the field of efficient solar energy utilization. Copper phosphides become an ideal material to serve as the cocatalysts during photocatalytic hydrogen evolution by virtue of the lower prices. In this study, we synthesized graphitic carbon nitride (g-C3N4) based catalysts loaded with copper phosphide (Cu3P, Cu97P3), which exhibit superior performance in photocatalytic H2 evolution. Ultraviolet (UV)-visible spectroscopy illustrated that the absorption of light strengthened after the loading of copper phosphide, and the time-resolved transient photoluminescence (PL) spectra showed that the separation and transfer of the photoexcited carriers greatly improved. Moreover, both copper phosphide/g-C3N4 photocatalysts exhibited a relatively high H2 evolution rate: Cu3P/g-C3N4 (maximum 343 μmol h−1 g−1), Cu97P3/g-C3N4 (162.9 μmol h−1 g−1) while copper phosphide themself exhibit no photocatalytic activity. Thus, the copper phosphides (Cu3P, Cu97P3) work as a cocatalyst during photocatalytic H2 evolution. The cycling experiments illustrated that both copper phosphide/g-C3N4 photocatalysts perform excellent stability in the photocatalytic H2 evolution. It is worth noting that while the NaH2PO2 was heated in the tube furnace for phosphorization to obtain Cu3P, the excessive PH3 could pass through the solution of CuSO4 to obtain Cu97P3 at the same time, which significantly improved the utilization of PH3 and reduced the risk of toxicity. This work could provide new strategies to design photocatalysts decorated with copper phosphide for highly efficient visible-light-driven hydrogen evolution.