A well-defined amphiphilic graft copolymer, poly(6-methyl-1,2-heptadien-4-ol)-g-poly(2-(dimethylamino)ethyl methacrylate) (PMHDO-g-PDMAEMA), has been synthesized by the combination of living coordination polymerization, single electron transfer-living radical polymerization (SET-LRP), and the grafting-from strategy. PMHDO backbone containing double bonds and pendant hydroxyls was first prepared by [(3-allyl)NiOCOCF3]2-initiated living coordination polymerization of 6-methyl-1,2-heptadien-4-ol (MHDO) followed by treating the pendant hydroxyls with 2-chloropropionyl chloride to give PMHDO-Cl macroinitiator. SET-LRP of 2-(dimethylamino)ethyl methacrylate (DMAEMA) was performed in THF/H2O using PMHDO-Cl as macroinitiator and CuCl/Me6TREN as catalytic system to afford the well-defined PMHDO-g-PDMAEMA graft copolymer with a narrow molecular weight distribution (Mw/Mn = 1.28). The grafting density was as high as 92%. The critical micelle concentration (cmc) in water was determined by fluorescence probe technique and the micellar morphology was preliminarily explored by transmission electron microscopy. (c) 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013, 51, 1880-1886