Liquid–liquid phase asymmetric Darzens condensations were carried out in the presence of d-glucose- and d-mannose-based crown ethers 1 and 2 as the catalyst. The use of d-glucose-based lariat ether 1 as the catalyst gave the best results. The reaction of 4-phenyl-α-chloroacetophenone, 2-chloro-1-tetralone, and 2-chloro-1-indanone with various aromatic aldehydes afforded the corresponding aromatic α,β-epoxyketones in moderate to high enantiomeric excess (ee up to 96%) under mild reaction conditions. The substituents of the benzaldehyde used as the reactants had a significant impact on the chemical yields and enantiomeric excess. The absolute configuration of some epoxyketone products was determined by single-crystal X-ray analysis.