A novel enantioselective Michael addition of malononitrile to trans-β-nitroolefins in the presence of bifunctional amine thiourea organocatalyst is developed. The Michael reaction catalyzed by amine thioureas containing both central and axial chiral elements proceeded smoothly and provided the desired adducts with high yields (up to 96% yield) and moderate enantioselectivities (up to 83% enantiomeric excess). Chirality, 2011. © 2011 Wiley-Liss, Inc.