Abstract Catalytic asymmetric epoxidation of α,β-unsaturated N-acylpyrroles as monodentate and activated ester equivalent acceptors is described. A Sm( O- i-Pr) 3/( R)-H 8-BINOL complex promoted the epoxidation reaction to afford products in high yield (up to quant) and high enantiomeric excess (up to >99.5% ee). Reaction proceeded smoothly using cumene hydroperoxide (CMHP) with low explosive hazard, and completed within 0.2–0.5 h with 5 mol % catalyst. Catalyst loading was successfully reduced to as little as 0.02 mol %. The N-acylpyrrole properties as well as efficient synthesis of α,β-unsaturated N-acylpyrroles are also described.