Selected perfluorinated surfactants were irradiated in aqueous hydrogen peroxide solutions using artificial sunlight to study transformation under aquatic environmental conditions. Indirect photolysis mediated by hydroxyl radical was observed for N-ethyl perfluorooctane sulfonamidoethanol (N-EtFOSE), N-ethyl perfluorooctane sulfonamido acetate(N-EtFOSAA), N-ethyl perfluorooctane sulfonamide (N-EtFOSA), and perfluorooctane sulfonamide acetate (FOSAA). An upper limit for the bimolecular reaction rate constant for reaction of •OH and N-EtFOSAA was determined to be (1.7 ± 0.7) × 109 M-1s-1. A proposed reaction pathway for degradation of the parent perfluorochemical, N-EtFOSE, to the other perfluoroalkanesulfonamides and perfluorooctanoate (PFOA) was developed and includes oxidation and N-dealkylation steps. As they did not undergo additional degradation, perfluorooctane sulfonamide (FOSA) and PFOA were the final degradation products of hydroxyl radical-initiated oxidation. UV-visible absorption spectra for the perfluorochemicals, showing absorbance in the UV region below the range of natural sunlight, are also reported. In sunlit environments, indirect photolysis of perfluorochemicals is likely to be important in the determination of their environmental fate given the slow rates expected for biotransformation and weak sorption. Photolytic conversion of perfluorochemicals into refractory perfluorinated acids, mainly PFOA, could mean that a significant fraction of these compounds will accumulate in the world's oceans.