Alcohols are among the most abundant feedstock chemicals with advantages such as low cost, benchstability, non-toxicity, structural diversity, and broad renewable availability from biomass and other natural sources. These characteristics render alcohols excellent precursors for alkyl radicals . In this context, N-alkoxyphthalimides, which can be readily prepared by a single-step alcohol decoration, have evolved as versatile alkyl radical precursors via homolytic cleavage and the follow-up β-scission or 1,5hydrogen atom transfer (HAT) process . Inspired by advances in N-alkoxyphthalimide chemistry and motivated by the gap in selective construction of both gem-difluoroalkenes and trifluoromethyl alkanes, we report herein a practical, visible-light-induced Eosin Y-catalyzed defluorinative alkylation reaction and catalyst-free electron donor-acceptor (EDA)-mediated . hydroalkylation reaction. These reactions use readily available alcohol-derived N-alkoxyphthalimides and α-trifluoromethyl olefins as starting materials, providing a green and efficient synthetic strategy for selective construction of both gemdifluoroalkenes and trifluoromethyl alkanes (Scheme 1c). Specifically, we selected Eosin Y as the ideal photocatalyst, owing to its low cost (~$100/kg), ease of handling, excellent photocatalytic performance, and complete absorption in the visible-light region .