Enzymatic hydrolyses of the sigma-symmetric dicarboxylic diesters bearing a sulfinyl group as the prochiral center were examined by employing porcine liver esterase and procine pancreatic lipase. Eventually, their chiral half esters were elaborately obtained as the corresponding chiral phenacyl esters. The stereochemistry of the chiral half esters was determined by the X-ray analysis and their chemical correlations.