C2-symmetric chiral bisformamides have been shown to catalyze the asymmetric one-pot, three-componentStrecker reaction, which produced the α-amino nitriles in excellent yields (up to 99%) with goodenantioselectivities (up to 86% ee). Optically pure products could be obtained after a single recrystallization.A possible transition state (TS1) has been proposed to explain the origin of asymmetric inductivity andreactivity according to the geometry of catalyst 2a optimized at the B3LYP/6-31G(d) level and the absoluteconfiguration of product 4a.