A novel well-defined amphiphilic graft copolymer of poly(ethylene oxide) as main chain and poly(methyl acrylate) as graft chains is successfully prepared by combination of anionic copolymerization with atom transfer radical polymerization (ATRP). The glycidol is protected by ethyl vinyl ether first, then obtained 2,3-epoxypropyl-1-ethoxyethyl ether (EPEE) is copolymerized with EO by initiation of mixture of diphenylmethyl potassium and triethylene glycol to give the well-defined poly(EO-co-EPEE), the latter is deprotected in the acidic conditions, then the recovered copolymer [(poly(EO-co-Gly)] with multi-pending hydroxyls is esterified with 2-bromoisobutyryl bromide to produce the ATRP macroinitiator with multi-pending activated bromides [poly(EO-co-GlY)((ATRP))] to initiate the polymerization of methyl acrylate (MA). The object products and intermediates are characterized by NMR, MALDI-TOF-MS, FT-IR, and SEC in detail. In solution polymerization, the molecular weight distribution of the graft copolymers is rather narrow (M-w/M-n < 1.2), and the linear dependence of Ln [M-0]/[M] on time demonstrates that the MA polymerization is well controlled. (c) 2006 Elsevier Ltd. All rights reserved.