Enantioselective transformation of strong electron-withdrawing acyclic α-trifluoromethylimines to α-trifluoromethylamines through a ruthenium-catalyzed asymmetric transfer hydrogenation has been developed. The method described here is a facile catalytic process with sodium formate as a hydrogen resource and water-dimethylformamide as a cosolvent. The benefit of this enantioselective transformation affords a series of chiral α-trifluoromethylamines with high yields and excellent enantioselectivities (93-99% ee) under mild reaction conditions.