Hyperbranched polyglycerol containing terminal five-membered cyclic carbonate groups has been obtained by anionic polymerization of glycidol and then in the reaction of its terminal vicinal hydroxyl groups with dimethyl carbonate in the presence of potassium carbonate. The remaining OH groups of the polymer were protected in the reaction with acetic anhydride to reduce polymer hydrophilicity and increase miscibility with the epoxy resin. A strong decrease in viscosity was observed after esterification, from 73 to 3.6 Pa s. The product (HBPG 3) was used for modification of the bisphenol A based epoxy resin. The epoxide-cyclic carbonate compositions were cured using a polyamine hardener (TETA) in a one-step procedure. Thermal and mechanical properties of the cured compositions were characterized and compared with the parent epoxy resin. The optimal mechanical properties were obtained for the compositions containing HBPG 3 when phase separation takes place. The mechanical properties are discussed in terms of the morphology observed by SEM. (c) 2007 Elsevier Ltd. All rights reserved.