In this work, a photocatalytic fuel cell (PFC) with membrane electrode assembly (MEA) structure was designed for simultaneous organic compounds degradation and electricity generation. For the photoanode, the TiO2 with the quantum-dot sensitization by CdS-ZnS was used to broaden the absorption spectrum to visible light. For the cathode, an air-breathing mode was utilized to enhance the oxygen transport. The performance of the developed PFC was evaluated under different operation conditions, including the light intensity, liquid flow rate, concentrations of electrolyte and organics. Results indicated that the designed PFC could yield good performance. The increase of the light intensity and electrolyte concentration could improve the PFC performance. It is also found that when the flow rate was increased, the PFC performance dropped down in the testing range. Too high organics concentration led to the decrease of the PFC performance.