Abstract A first catalytic enantioselective intermolecular radical aminotrifluoromethylation of alkene with hydrazine and Togni's reagent by Cu(I)/CPA cooperative catalysis has been reported, accessing diversely substituted CF 3 ‐containing enantioenriched diarylmethylamines bearing an α ‐tertiary stereocenter with high enantioselectivity and excellent chemoselectivity. The highly asymmetric induction of C−N bond formation between hydrazine and the carbocation intermediate was achieved by using a CPA catalyst via hydrogen‐bonding and ion pair interaction.