Herein, we report a Cu-mediated trifluoromethylation of carbonyl-type compounds and unactivated olefins enabled by visible-light irradiation via σ C(sp3)−C bond-functionalization. The reaction is distinguished by its modularity, mild conditions and wide scope—even in the context of late-stage functionalization—thus offering a complementary approach en route to valuable C(sp3)−CF3 architectures from easily accessible precursors.