A photocatalytic three-component reaction of α-trifluoromethyl alkenes, electron-rich alkenes, and sodium sulfinates for the synthesis of gem-difluoroalkenes in a radical/polar crossover manner was developed. Due to the strong electron-withdrawing nature of the sulfonyl group, the resultant gem-difluoroalkenes can be converted into various monofluorocyclopentenes via intramolecular base-mediated SNV reactions in one pot.