A perfluorooctanoic acid (PFOA), as the most important representative of perfluorocarboxylic acids (PFCAs), is environmentally persistent and bioaccumulative. Among treatment techniques for PFOA decomposition, photocatalytic degradation of PFOA has received considerable attention. A series of candidate photocatalytic materials, including TiO2-, carbonaceous-, Ga2O3-, In2O3-based, etc., have been successfully proposed to eliminate PFOA. Overall, there are two types of mechanisms for photocatalytic degradation of PFCAs, including conventional mechanism and charge transfer mechanism. For a conventional mechanism, the mechanism of PFOA photodegradation over bulk TiO2 via two pathways: photo-redox and beta-scission. For the charge transfer mechanism, the PFOA degradation pathway in water-soluble H3PW12O40 is mainly via charge-transfer excited complex ([PW12O40](3-*)). Finally, attention on critical challenges and prospects for photodegradation of PFOA are also intensified. (c) 2020 Society of Chemical Industry