The enzymatic esterification of glycerol with dicarboxylic acids or esters was studied to produce mono- and/or diesterified glycerol adducts. Such materials are useful synthons in the synthesis of biodegradable polymers and surfactants. In this work two strategies were studied for preparing these prepolymeric glycerol derivatives: the lipase-catalyzed esterification of free glycerol with diacids or esters and the reaction of supported or protected glycerol with diesters. For example, reaction of isopropylidene glycerol with dimethyl sebacate gave a >95% yield of isopropylidene glycerol-monomethyl sebacate ester. Reaction of glycerol supported on silica with dimethyl adipate gave a 40% yield of glycerol-monomethyl adipate ester. Best yields of glycerol-mono- and diesters (70% and 10%, respectively) were obtained by direct esterification of free glycerol with a diester in a solvent-free system containing small amounts of water (<4%).