A copper-catalyzed regioselective net hydroamination of 1-trifluoromethylalkenes with hydrosilanes and hydroxylamines has been developed. The judicious choice of ligand and additive suppresses the conceivable but undesired β-F elimination of an α-CF3-substituted organocopper intermediate, leading to targeted α-trifluoromethylamines in good yields with excellent regioselectivity. Additionally, with an appropriate chiral bisphosphine ligand, the enantioselective reaction is also possible to deliver optically active α-trifluoromethylamines of high potential in medicinal and pharmaceutical chemistry.