WO3 photoelectrode should have high photoactivity and stability for application in solar water splitting. By introducing Bi3+ ions, a highly ordered (002)-oriented WO3 film with a high photocurrent was easily prepared on FTO glass by spin coating a simple Bi-doped peroxotungstic acid (PTA) gel followed by calcination. In situ XRD, pole figures, and HR-TEM were performed to elucidate the formation process and epitaxial properties. The flat Bi-WO3 film achieved a remarkable photocurrent density of 2.06 mA cm(-2) at 1.5 V vs. Ag/AgCI. By introducing intermittent short-time negative polarization (ISNP) into the process of PEC water splitting, the 03 gas product yield is enhanced by ca. 75% with high faradaic efficiency, as ISNP can efficiently eliminate peroxo species on the surface of the WO3 film. This demonstrates that ISNP can enhance the photostability and phoinactivity of WO3 films.