The controlled free-radical homopolymerization of ethyl alpha-hydroxymethylacrylate and copolymerization with methyl methacrylate were performed in chlorobenzene at 70 degrees C by the reversible addition-fragmentation chain transfer polymerization technique with 2,2'-azobisisobutyronitrile as the initiator. 2-Phenylprop-2-yl dithiobenzoate and 2-cyanoprop-2-yl dithiobenzoate were used as chain-transfer agents in the homopolymerization, whereas only the former was used in the copolymerization. All reactions presented pseudolinear kinetics. The effect of the monomer feed ratio on the copolymerization kinetics was examined. The conversion level decreased when the proportion of ethyl alpha-hydroxymethylacrylate in the monomer feed was larger. Kinetic studies indicated that the radical polymerizations proceeded with apparent living character according to experiments, demonstrating an increase in the molar mass with the monomer conversion and a relatively narrow molar mass distribution. All copolymers were statistical in chain structure, as confirmed by determinations of the monomer reactivity ratios. The monomer reactivity ratios were determined, and the Mayo-Lewis terminal model provided excellent predictions for the variations of the intermolecular structure over the entire conversion range. Additionally, the chemical modification of poly(ethyl alpha-hydroxymethylacrylate) was carried out to introduce glucose pendant groups into the structure. (c) 2006 Wiley Periodicals, Inc.