The visible-light-driven, phase-transfer-catalyzed, enantioselective perfluoroalkylation and trifluoromethylation of cyclic β-ketoesters is described. The photoorganocatalytic process, which occurs at ambient temperature and under visible light illumination, is triggered by the photochemical activity of in situ-generated electron donor−acceptor complexes, arising from the association of chiral enolates and perfluoroalkyl iodides. Preliminary mechanistic studies are reported.