Chiral γ-aminobutyric acid (GABA) derivatives are the normal inhibitory neurotransmitters in the mammalian central nervous system. In this paper, enantiopure GABA derivatives 6 were synthesized via reduction/cyclization/hydrolysis cascade reactions from the highly enantioselective β-aryl-γ- ni-troalkanes Michael adducts 4, which was obtained from asymmetric Michael addition of S, S’-diphenyldithiomalonate 2 to trans-β-nitroolefins 1, using novel chiral cinchona alkaloid-derived thioureas 3 as the organocatalysts. This synthesis represents an efficient, highly selective and environmental benign methodology for GABA derivatives.