Graft copolymers having poly(methyl methacrylate), PMMA, backbone and polystyrene, PS, polyisoprene, PI, poly(ethylene oxide), PEO, poly(2-methyl-1,3-pentadiene), P2MP, and PS-b-PI branches were prepared using the macromonomer methodology and high-vacuum techniques. The methacrylic macromonomers, mMM, were synthesized by anionic polymerization, whereas their homopolymerization and copolymerization with MMA were performed by metallocene catalysts. Relatively high macromonomer conversions were obtained in all cases. The parameters affecting the polymerization characteristics were examined. Well-defined poly(butyl methacrylate)-b-poly(methyl methacrylate) block copolymers were prepared for the first time by sequential addition of monomers starting from n-butyl methacrylate. The samples were characterized by size exclusion chromatography, SEC, H-1 and C-13 NMR spectroscopy, low-angle laser light scattering, LALLS, and differential scanning calorimetry, DSC.