A metal-free photochemical strategy for the direct aromatic perfluoroalkylation of phenols is reported. This operationally simple approach occurs at ambient temperature and under illumination by a fluorescent light bulb. The chemistry is driven by the ability of phenolate anions, transiently generated upon deprotonation of phenols, to directly reach an electronically excited state upon light absorption while successively triggering the formation of reactive radical species from perfluoroalkyl iodides. Preliminary mechanistic studies are reported.