Perfluorinated alcohols (PFOHs) are thermally unstable and degrade via loss of HF, ultimately forming perfluorocarboxylic acids. Experiments and calculations of the high activation barrier for the decomposition Of CF3OH suggest that the reaction occurs exclusively heterogeneously, perhaps with the involvement of water. Here, we use density functional theory calculations to show that PFOHs may readily complex with water and are expected to be present as a few percent of the total PFOH concentration under ambient atmospheric conditions. The presence of water lowers the HF elimination barrier sufficiently that excitation to low-lying O-H vibrational overtone levels (v(OH) >= 3) may cause reaction. Photolysis rate constants for CF3OH center dot H2O and CF3CF2OH center dot H2O were estimated to be 6.1 x 10(-8) and 5.6 x 10(-8) s(-1), respectively. PFOH-water complexes should undergo degradation much faster than the corresponding gas-phase unimolecular decomposition of PFOHs, which requires excitation into the v(OH) = 5 or 6 vibrational level. Overtone-driven (gas-phase reactions of PFOH-water complexes could be moderately competitive with heterogeneous reactions with water in dry locations. Overtone-induced degradation of PFOHs is likely a modest atmospheric source of PFCAs to the environment.