A method for producing optically active glycol derivatives by biochemical resolution which comprises contacting a racemic ester of the general formula 1 ##STR1## (wherein R.sub.1 is an aliphatic hydrocarbon group of 1 to 16 carbon atoms, R.sub.2 is an aliphatic hydrocarbon group of 1 to 8 carbon atoms, and R.sub.3 is an aromatic hydrocarbon group such as phenyl, tolyl or naphtyl) with a microorganism- or animal organ-derived enzyme having stereoselective hydrolytic activity to asymmetrically hydrolyze said racemic ester of general formula 1 to produce an optically active alcohol of general formula 2* ##STR2## (wherein R.sub.1 and R.sub.3 have the same meanings as defined above) and an unreacted ester of the general formula 1* ##STR3## (wherein R.sub.1, R.sub.2 and R.sub.3 have the same meanings as defined hereinbefore), separating the optically active compounds from each other, hydrolyzing said ester of general formula 1* to give an optically active glycol derivative which is antipodal to the alcohol of general formula 2* and, then, isolating the same optically active glycol derivative. The invention provides a method for producing optically active glycol derivatives, which is expedient, does not require costly reagents and is suited to commercial scale production.