AbstractUpon treatment of chiral β-trifluoromethyl-α,β-unsaturated N-acylated oxazolidin-2-ones with a range of alcohols using phosphazene base as a catalyst, the unexpected cascade esterification/stereoselective aza-Michael addition was observed. The reactions proceeded with high diastereoselectivities (up to >99:1) to give a series of enantioenriched aza-Michael addition products in good to high yields. The structure and stereochemistry of the representative aza-Michael adduct were confirmed by X-ray crystal structure analysis. The plausible mechanism was proposed on the basis of the experimental results.The synthetic transformations of chiral aza-Michael addition products were also demonstrated highlighting the synthetic application of the present work.