In this work, a membrane electrode assembled photoelectrochemical cell (PEC) is developed for the electricity generation by degrading the organic compounds. The photocatalyst is prepared by the incorporation of mesoporous silica SBA-15 into TiO2 and the photosensitization of CdS-ZnS to enhance the photoanode performance, while the cathode employs the air-breathing mode to enhance the oxygen transport. The experimental results show that the developed PEC exhibits good photoresponse to the illumination and the appropriate SBA-15 mass ratio in the photoanode enables the enhancement of the performance. It is also shown that the developed PEC yields better performance in the alkaline environment than that in the neutral environment. Increasing the KOH concentration can improve the cell performance. There exist optimal liquid flow rate and organics concentration leading to the best performance. Besides, it is found that increasing the light intensity can generate more electron-hole pairs and thus enhance the cell performance. These results are helpful for optimizing the design.