The asymmetric aza-Henry reaction of α-substituted nitroacetates and N-Boc imines was achieved with a new-type thiourea-guanidine bifunctional organocatalyst. The novel transformations exhibited high diastereoselectivities, and the adducts bearing adjacent quaternary and tertiary chiral centers were generally obtained in moderate to good enantioselectivities (up to 88% ee).