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. Shining light: An operationally simple protocol for the direct aromatic perfluoroalkylation and trifluoromethylation of α‐cyano arylacetates requires the irradiation by visible light at ambient temperature. This metal‐free reaction 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.