The invention provides two TiO2-based photocatalytic composite-electrode fuel cells with different structures, and an apparatus used for processing organic wastewater. The apparatus comprises a speed regulator, a driving motor, a photocathode shaft, a photocathode rotary table, plural sheets of photo-anodes, a fuel cell reaction tank, and an excitation light source. The apparatus is characterized in that: a draft-tube is arranged on the bottom of the fuel cell reaction tank; and a water pump is arranged on the draft-tube. The water pump is started; the organic wastewater is transferred from the draft-tube on the bottom of the photo-anode reaction tank to the top of the photo-anodes, and flows down, such that a liquid film is formed on the surfaces of the photo-anodes; meanwhile, the driving motor is started, the rotation speed of the photocathode rotary table is controlled by the speed regulator, such that the photocathode rotary table rotates, and a liquid film is also formed on the surface of the photocathode. Photo-anodes with different structures are adopted, such that the processing efficiency of the organic wastewater is improved. The photo-anodes are designed as rectangles, such that the liquid film formed by the water flow on the surfaces of the photo-anodes is more uniform, and the organic wastewater can be more effectively processed by using the TiO2-based photocatalytic composite-electrode fuel cell.