A series of well-defined amphiphilic graft copolymer containing hydrophobic polyallene-based backbone and hydrophilic poly(2-(diethylamino)ethyl acrylate) (PDEAEA) side chains was synthesized by sequential living coordination polymerization of 6-methyl-1,2-heptadiene-4-ol (MHDO) and single electron transfer-living radical polymerization (SET-LRP) of 2-(diethylamino)ethyl acrylate (DEAEA). Ni-catalyzed living coordination polymerization of MHDO was first performed in toluene to give a well-defined double-bond-containing poly(6-methyl-1,2-heptadiene-4-ol) (PMHDO) homopolymer with a low polydispersity (Mw/Mn = 1.10). Next, 2-chloropropionyl chloride was used for the esterification of pendant hydroxyls in every repeating unit of the homopolymer so that the homopolymer was converted to PMHDO-Cl macroinitiator. Finally, SET-LRP of DEAEA was initiated by the macroinitiator in tetrahydrofuran/H2O using CuCl/tris(2-(dimethylamino)ethyl)amine as catalytic system to afford well-defined PMHDO-g-PDEAEA graft copolymers (Mw/Mn <= 1.22) through the grafting-from strategy. The critical micelle concentration (cmc) was determined by fluorescence spectroscopy with N-phenyl-1-naphthylamine as probe and the micellar morphology was visualized by transmission electron microscopy. (c) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013