In conclusion, we have developed a novel and practical method for the selective synthesis of both gemdifluoroalkenes and trifluoromethyl alkanes from α-trifluoromethyl olefins. By utilizing visible-light-induced Eosin Y-catalyzed defluorinative alkylation and catalyst-free electron donor-acceptor (EDA)mediated hydroalkylation, we demonstrated an efficient and green strategy to accommodate various primary, secondary, and tertiary functionalities under mild reaction conditions. The approach offers excellent chemo-selectivity, high yields, and broad substrate compatibility, making it a powerful tool for the syn-