The global occurrence and adverse environmental impacts of perfluorooctanoic acid (PFOA) have attracted wide attention. This study focused on the PFOA photodegradation by using photocatalyst TiO2 with peroxymonosulfate (PMS) activation. Aqueous PFOA (50 mg L-1) at the pH 3 was treated by TiO2/PMS under 300 W visible light (400-770 nm) or 32 W UV light (254 nm and 185 nm). The addition of PMS induced a significant degradation of PFOA under powerful visible light compared with sole TiO2. Under visible light, 0.25 g L-1 TiO2 and 0.75 g L-1 PMS in the solution with the initial pH 3 provided optimum condition which achieved 100% PFOA removal within 8 h. Under UV light irradiation at 254 nm and 185 nm wavelength, TiO2/PMS presented excellent performance of almost 100% removal of PFOA within 1.5 h, attributed to the high UV absorbance by the photocatalyst. The intermediates analysis showed that PFOA was degraded from a long carbon chain PFOA to shorter chain intermediates in a stepwise manner. Furthermore, scavenger experiments indicated that SO4•-radicals from PMS and photogenerated holes from TiO2 played an essential role in degrading PFOA. The presence of organic compounds in real wastewater reduced the degradation efficacy of PFOA by 18-35% in visible/TiO2/PMS system. In general, TiO2/PMS could be an ideal and effective photocatalysis system for the degradation of PFOA from wastewater using either visible or UV light source.