Well-defined graft copolymers with poly(methyl methacrylate) backbone and poly(styrene) (PS), poly(isoprene) (PI), or poly(dimethylsiloxane) (PDMS) branches were synthesized by combining anionic and metallocene catalyzed polymerization. The synthetic strategy involves the preparation of methacryloyl macromonomers of PS, PI, and PDMS by anionic polymerization, followed by copolymerization with methyl methacrylate using the highly reactive catalytic system CP2ZrMe2/B(C6F5)(3)/ZnEt2 The macromonomers and the fractionated graft copolymers were characterized by size exclusion chromatography, low-angle laser light scattering, and H-1 NMR spectroscopy.