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Phosphides exhibit relatively low overpotential for electrical hydrogen evolution reaction (HER), thus they have great potential to be used for cocatalyst for photocatalyst. Cu₃P, as a p-type semiconductor, tends to form a p-n junction with an n-type photocatalyst. Typically, it is treated as a sensitizer to extend the light absorption. However, its function and work mechanism are not fully understood in the catalyst system. In this report, we synthesized g-C₃N₄ and loaded Cu₃P nanoparticle on its surface. The photoluminescence (PL) spectra, photocurrent and electrochemical impedance spectra confirm the Cu₃P greatly enhance the charge separation process. Electrochemical HER results indicate that the composites have lower over-potential for HER. These results confirm the Cu₃P works as a cocatalyst in the system, not a sensitizer. Further, we tracked the photogenerated electron transfer direction via photodeposition …