A facile and regioselective enzymatic synthesis approach to prepare polymerizable lipophilic chlorphenesin vinyl esters was developed in this research. The influence of different organic solvents, enzyme sources, reaction time and the acylation reagent on the synthesis of chlorphenesin vinyl esters was investigated. Then the polymerizable monomers 1-O-vinylsuccinyl-chlorphenesin (OVSC) and 1-O-vinyladipoyl-chlorphenesin (OVAC) were homopolymerized using AIBN as the initiator. The obtained polymeric prodrugs were characterized with IR, NMR and GPC analyzes. The poly-OVSC has M-n Of 1.35 x 10(4) and M-w/M-n of 1.95, and the poly-OVAC has M-n of 2.37 x 10(4) and M-w/M-n of 4.30. Moreover, 6-O-vinyladipoyl-D-glucose (OVAG), a biocompatible monomer, was copolymerized with OVSC and OVAC. Polymeric prodrugs of chlorphenesin with saccharide branches were successfully obtained with high molecular weight. (c) 2007 Elsevier Ltd. All rights reserved.