A series of new well-defined amphiphilic graft copolymers containing hydrophobic poly(tert-butyl acrylate) backbone and hydrophilic poly(ethylene oxide) side chains were reported. Reversible addition-fragmentation chain transfer homopolymerization of tert-butyl 2-((2-bromopropanoyloxy)methyl)acrylate was first performed to afford a well-defined backbone with a narrow molecular weight distribution (Mw/Mn = 1.07). The target poly(tert-butyl acrylate)-g-poly(ethylene oxide) (PtBA-g-PEO) graft copolymers with low polydispersities (Mw/Mn = 1.181.26) were then synthesized by atom transfer nitroxide radical coupling or single electron transfer-nitroxide radical coupling reaction using CuBr(Cu)/PMDETA as catalytic system. Fluorescence probe technique was employed to determine the critical micelle concentrations (cmc) of the obtained amphiphilic graft copolymers in aqueous media. Furthermore, PAA-g-PEO graft copolymers were obtained by selective acidic hydrolysis of hydrophobic PtBA backbone while PEO side chains kept inert. (c) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012