Perfluorinated chemicals (PFCs) are distributed throughout the environment. In the case of perfluorinated alkyl carboxylates and sulfonates, they can be classified as persistent organic pollutants since they are resistant to environmentally relevant reduction, oxidation, and hydrolytic processes. With this in mind, we report on the reductive defluorination of perfluorobutanoate, PFBA (C3F7CO2-), perfluorohexanoate, PFHA (C5F11CO2-), perfluorooctanoate, PFOA (C7F15CO2-), perfluorobutane sulfonate, PFBS (C4F9SO3-), perfluorohexane sulfonate, PFHS (C6F13SO3-), and perfluorooctane sulfonate, PFOS (C8F17SO3-) by aquated electrons, e(aq)(-), that are generated from the UV photolysis (lambda = 254 nm) of iodide. The ionic headgroup (-SO3- vs -CO2-) has a significant effect on the reduction kinetics and extent of defluorination (F index = -[F-](produced)/ [PFC](degraded)). Perfluoroalkylsulfonate reduction kinetics and the F index increase linearly with increasing chain length. In contrast, perfluoroalkylcarboxylate chain length appears to have a negligible effect on the observed kinetics and the F index. H/F ratios in the gaseous fluoro-organic products are consistent with measured F indexes. Incomplete defluorination of the gaseous products suggests a reductive cleavage of the ionic headgroup occurs before complete defluorination. Detailed mechanisms involving initiation by aquated electrons are proposed.