An enantioselective Michael addition between N-2,2,2-trifluoroethylisatin ketimines and ethylene sulfonyl fluoride has been disclosed. This method provides a facile strategy to access a range of structurally diverse isatin-derived α-(trifluoromethyl)imine derivatives with excellent yields and enantioselectivities. The intriguing combination of α-(trifluoromethyl)amine and sulfonyl fluoride groups leads to the valuable candidates for the drug discovery.