We report the first examples of catalytic enantioselective benzilic ester rearrangement reaction. In the presence of a catalytic amount of Cu(OTf)(2) and a chiral box ligand under mild conditions, reaction of 2,3-diketoesters with alcohols afforded structurally diverse alpha-aryl(alkyl) substituted-alpha-hydroxy malonates (tartronic esters) in good to excellent yields with high enantioselectivities. Preliminary mechanistic studies indicated that hemiketalization, rather than the dynamic kinetic resolution of hemiketal, was the enantiodetermining step under our reaction conditions.