We report herein an unprecedented protocol for aminotrifluoromethylation of alkenes. With Cu(OTO2 as the catalyst, the reaction of alkenes, (bpy)Zn(CF3)(2), and N-fluorobis(benzenesulfonyl)imide (NFSI) at room temperature provides the corresponding aminotrifluoromethylation products in satisfactory yields with high regioselectivity opposite to those driven by CF3 radical addition. The method exhibits a broad substrate scope and wide functional group compatibility. A mechanism involving N-radical addition to alkenes followed by trifluoromethylation of alkyl radicals is proposed.