A method for reductive degradation of perfluorooctanoic acid (PFOA) was established by using a sulfite/UV process. This process led to a PFOA removal of 100% at about 1 h and a defluorination ratio of 88.5% at reaction time of 24h under N-2 atmosphere, whereas the use of either UV irradiation or SO32- alone induced little defluorination of PFOA under the same conditions. It was confirmed that the reductive defluorination of PFOA was achieved by hydrated electrons being generated from the photo-conversion of SO32- as a mediator. Theoretical reaction kinetic analysis demonstrated that the generation of hydrated electrons was promoted by increasing either SO32- concentration or solution pH, leading to the acceleration of the PFOA defluorination. Accompanying the reduction of PFOA, a small amount of short-chain perfluorocarboxylic acids, less fluorinated carboxylic acids and perfluorinated alkyl sulfonates were generated, all of which were able to be further degraded with further releasing of fluoride ions. Based on the generation, accumulation and distribution of intermediates, hydrated electrons induced defluorination pathway of PFOA was proposed in a sulfite-mediated UV photochemical system. (C) 2013 Elsevier B.V. All rights reserved.