Herein we describe the synthesis of block and graft copolymers made from several higher alpha-olefins, and in some cases styrene and methyl methacrylate, through the use of metallocene catalysts as well as the combination of metallocene and atom transfer radical polymerization (ATRP). The C-s-symmetry hafnium metallocene catalyst [(p-Et3Si)Ph](2)C-(2,7-di-tert-BuFlu)(Cp)Hf(CH3)(2) with tetrakis(pentafluorophenyl) borate dimethylanilinium salt, ([B(C6F5)(4)](-)[Me-2-NHPh](+)), as cocatalyst, in the presence of trioctylaluminum has been used for the synthesis of the following diblock copolymers and triblock terpolymers by sequential polymerization: poly[(hexene-1)-b-(tetradecene-1)], polyRoctene-1)-b-(tetradecene-1)], poly[(hexene-1)-b-(methyl methacrylate)], polyRoctene-1)-b-(methyl methacrylate)], poly[(hexene-1)-b-(octene-1)-b-(tetradecene-1)], poly[(hexene-1)-b-(octene-1)b-(decene-1)], and poly[(hexene-1)-b-(octene-1)-b-(methyl methacrylate)]. By combining the above metallocene catalyzed polymerization and ATRP, graft and block graft copolymers having either poly(tetradecene-1) or poly(octene-1) backbones and poly(rnethyl methacrylate) or polystrrene branches were synthesized. All samples were thoroughly characterized by size exclusion chromatography, SEC, H-1 and C-13 NMR spectroscopy, and low angle laser light scattering, LALLS, as well as differential scanning calorimetry, DSC.