The star graft copolymers with three arms composed of poly(ethylene oxide) (PEO) as main chain and polystyrene (PS) as side chains were prepared by sequential anionic ring-opening copolymerization of ethylene oxide and ethoxyethyl glycidyl ether (EEGE), and then atom transfer radical polymerization (ATRP) of styrene. The anionic ring-opening copolymerization of EO and EEGE was carried out using 2-ethyl-2-hydroxymethyl-1,3-propanediol as trifunctional initiator and diphenylmethyl potassium (DPMK) as deprotonating agent. The resulting three-arm star copolymer [poly(EO-co-EEGE)](3) could be easily hydrolyzed to unmask the pendant hydroxyl groups without affecting the PEO chains. The switch from the first to the second mechanism was completed by the reaction of the multi-pendant hydroxyl groups of three-arm PEO chain with 2-bromoisobutyryl bromide. The obtained poly(ethylene oxide-co-2-bromoisobutyryloxyglycidyl ether), [poly(EO-co-BiBGE)](3), was used as macroinitiators to initiate the polymerization of styrene in bulk at 90 C by ATRR The final products and intermediates were characterized by NMR, SEC and IR in detail. The amphiphilic star graft copolymers synthesized can form micelles in water. The critical micelle concentration (cmc) determined by fluorescence spectra was about 5 x 10(-7) g/mL. Sphere micelles were observed by transmission electron microscopy (TEM) at low copolymer concentration (6 x 10(-5) g/mL), but the micelle shape became irregular when the copolymer concentration increased to 6 x 10(-4) g/mL. (c) 2007 Elsevier Ltd. All rights reserved.