The invention discloses a photocatalytic hydrogen peroxide generation and photocatalytic fuel cell coupling system. A groove-shaped cavity is formed in a reaction cavity body and is sealed by conductive glass, the front portion of the cavity is a reaction chamber, the rear portion is provided with a cathode chamber and an anode chamber arranged side by side and communicated mutually, a photocatalyst layer is arranged in the reaction chamber, a cathode catalyst layer is arranged in the cathode chamber, an anode photocatalyst layer is arranged in the anode chamber, and the photocatalyst layer, the cathode catalyst layer and the anode photocatalyst layer are supported on the conductive glass. The system integrates photocatalytic hydrogen peroxide generation and simultaneous power generation of organic matter from photocatalytic fuel cell disposal, is simple in structure and low in cost and has the advantages of being free of membranes, large in specific surface area, high in mass transfer efficiency, accurate in flow control, short in contact time, easy to enlarge, uniform in lighting, small in optical path loss and the like, and the performance is effectively improved. The organic matter in water can be utilized to generate power, environmental pollution can be controlled, and meanwhile electric energy can be also obtained.