This article aims to elucidate on usefulness of vacuum ultraviolet (VUV) for photoreductive degradation of perfluorooctanoic acid (PFOA), a representative perfluorinated compound (PFC), in water for the first time. Bench-scale tests were conducted on oxidative and reductive (with aquated electron: e aq − ) mineralization of PFOA using low-pressure UV (LPUV) lamps and potassium iodide. Unlike with 254 nm wavelength (UVC), the reductive mineralization with VUV was very inefficient compared to the corresponding oxidative mineralization. The inefficiency is attributed to low reactivity of e aq − with PFOA and its fluorinated products than that of 185 nm photons. Direct VUV photolysis of PFOA and its products in reductive reaction conditions was not apparent due to a very big difference in reactivity of 185 and 254 nm photons with iodide. The results demonstrated that highly energetic VUV photons are not suitable for photoreductive degradations of PFCs involving e aq − , but they can be best used for oxidative degradations. These findings should serve as an important reference on VUV usage to decompose refractory micropollutants.