A series of well-defined graft copolymers with a polyallene-based backbone and polystyrene side chains were synthesized by the combination of living coordination polymerization of 6-methyl-1,2-heptadien-4-ol and atom transfer radical polymerization (ATRP) of styrene. Poly(alcohol) with polyallene repeating units were prepared via 6-methyl-1,2-heptadien-4-ol by living coordination polymerization initiated by [(eta(3)-allyl)NiOCOCF3](2) firstly, followed by transforming the pendant hydroxyl groups into halogen-containing ATRP initiation groups. Grafting-from route was employed in the following step for the synthesis of the well-defined graft copolymer: polystyrene was grafted to the backbone via ATRP of styrene. The cleaved polystyrene side chains show a narrow molecular weight distribution (M-w/M-n = 1.06). This kind of graft copolymer is the first example of graft copolymer via allene derivative and styrenic monomer. (c) 2007 Wiley Periodicals, Inc.