A series of polyallene-based well-defined amphiphilic graft copolymers consisting of hydrophobic poly(6-methyl-1,2-heptadiene-4-ol) (PMHDO) backbone and hydrophilic poly(2-(dimethylamino)ethyl acrylate) (PDMAEA) side chains, was synthesized by the combination of living coordination polymerization and single-electron transfer living radical polymerization (SET-LRP). A double-bond-containing PMHDO backbone with pendant hydroxyls was prepared via [(η³-allyl)NiOCOCF₃]₂-initiated living coordination polymerization of a hydroxyl-containing allene derivative, 6-methyl-1,2-heptadiene-4-ol (MHDO). The pendant hydroxyls in the homopolymer were then treated with 2-chloropropionyl chloride to provide the PMHDO-Cl macroinitiator. Finally, the target PMHDO-g-PDMAEA well-defined graft copolymers were constructed through the grafting-from technique via SET-LRP of 2-(dimethylamino)ethyl acrylate (DMAEA) in acetone, a nonpolar solvent, initiated by the macroinitiator using CuCl/Me₆TREN as catalytic system. The narrow molecular weight distributions (M_w/M_n ≤ 1.18) and kinetics experiment showed the controllability of SET-LRP graft copolymerization of DMAEA. The critical micelle concentrations (cmc) of PMHDO-g-PDMAEA amphiphilic graft copolymers in aqueous solution were determined by fluorescence probe technique and the dependence of cmc on pH or salinity were also investigated. Micellar morphologies were visualized using transmission electron microscopy.