The catalytic enantio- and diastereoselective nitro-Mannich reaction of 伪-amido sulfones in the mixed solvent of toluene/H2O has been realized using a phase-transfer catalyst (PTC) derived from cinchona alkaloids and N-benzotriazole. It performed well over a wide range of substrates to give the desired products in good yields (up to 94%) with excellent enantioselectivities (up to 99% ee) and diastereoselectivities (up to 99:1).