The first example of diastereo- and enantioselective aza-MBH-type reaction was accomplished by the asymmetric synthesis of β-nitro-γ-enamines via a (1R,2R)-diaminocyclohexane thiourea derivative mediated tandem Michael addition and aza-Henry reaction in good yields (up to 95%) and high enantioselectivities (up to 91% ee) and diastereoselectivities (up to 1:99 dr).