Herein, we report a photoredox enabled defluorinative benzylation of trifluoromethyl alkenes with readily available alkylarenes, which provides convenient access to a series of structurally valuable benzylated gem-difluoroalkenes under mild reaction conditions. The synthetic value of this protocol has been demonstrated by the transformations of several substrates bearing drug moieties, gram-scale reactions, and various further derivatizations of the gem-difluoroalkene products. The preliminary mechanistic investigations suggest a reaction pathway with rate-determining benzyl C-H bond cleavage of toluene followed by benzylic radical formation.