We report here an operationally simple protocol for the direct aromatic perfluoroalkylation and trifluoromethylation of α-cyano arylacetates. This metal-free approach, which occurs at ambient temperature and under visible-light irradiation, is driven by the photochemical activity of electron donor-acceptor (EDA) complexes, formed in situ by the interaction of transiently generated enolates and perfluoroalkyl iodides. Preliminary mechanistic studies are reported.