A vinyl-terminated linear polyethylene (number-average molecular weight = 1800, weight-average molecular weight/ number-average molecular weight = 1.7, functionality = 92%) prepared by ethylene coordination polymerization was transformed into a monohydroxyterminated linear polyethylene by hydroalumination of the vinyl group with diisobutylaluminum hydride and subsequent oxidation and hydrolysis. This monohydroxy-terminated linear polyethylene was quantitatively converted into a linear polyethylene macromonomer with a terminal a-methacrylate group through esterification followed by dehydrobromination. A grafting-through atom transfer radical polymerization of the a-methacrylate-terminated poly-ethylene and styrene was performed to yield a well-defined polystyrene-graft-polyethylene copolymer. The number-average molecular weight of the graft copolymers, measured by gel permeation chromatography, was lower than the predetermined number-average molecular weight, presumably because of the intramolecular aggregation of polyethylene side chains. The a-methacrylate-terminated polyethylene content and number-average molecular weight I of polystyrene-graft-polyethylene were determined by H-NMR. (C) 2007 Wiley Periodicals, Inc.