A novel ternary hybrid catalyst with high-efficient photoelectrocatalytic property, namely composite photocatalyst of Zn-Ni-P@C3N4, was successfully designed and prepared for ethanol oxidation in alkaline media. A new electrode material for photoactivated fuel cells (PFC) was proposed. The Zn-Ni-P@C3N4 photoanode was used to generate electricity by catalytic oxidation of ethanol which was used as a direct fuel. The catalyst with ternary hybrid structure exhibiteds superior catalytic activity for ethanol oxidation. Compared to the nanostructures of Zn-P@C3N4 and Ni-P@C3N4 respectively, it possessed a more negative onset potential, higher oxidation peak current, a greater peak current density and minimum mass transfer resistance. These unique properties above were proved by a series of characterizations which include Cyclic Voltammetry (CV), Linear Scan Voltammetry (LSV), Current-time curves and Electrochemical Impedance Spectroscopy (EIS) etc. The excellent electrocatalytic and photoelectrocatalytic performance could be ascribed to the maximum interfacial contact of Ni2P, ZnP2 and g-C3N4, which decreases the agglomeration of nanostructures and effectively suppresses the recombination of photogenerated electron-hole. This work provides a strategy for the synthesis of superior semiconductor which can be used as an efficient visible-light-driven catalyst for photochemical synthesis and energy conversion. [GRAPHICS] .