The first efficient nonenzymatic acylative kinetic resolution of Baylis-Hillman adducts is reported. Chiral pyridine catalyst 1a and an optimized analogue 1e are capable of promoting the synthetically useful enantioselective acylation (the efficiency of which is outstanding for sp2-sp2 carbinol substrates, s= 3.5-13.1, ee up to 97%) of Baylis-Hillman adducts derived from recalcitrant precursors which are currently difficult to synthesize ...