This article demonstrates a facile and efficient method to combine olefin coordination polymerization with atom transfer radical polymerization (ATRP) for the synthesis of isotactic polypropylene (i PP) based functional diblock copolymers The chemistry involves a styryl capped i PP pre cursor prepared through the controlled consecutive chain transfer reaction first to 1 2 bis(4 vinylphenyl)ethane and then to hydrogen in propylene polymerization mediated by an isospecific metallocene catalyst The i PP precursor can be quantitatively transformed into i PP terminated with a 1 chlor oethylbezene group (i PP t Cl) by a straightforward hydro chlorination process using hydrogen chloride With the resultant i PP t Cl as a macroinitiator of ATRP methyl meth acrylate (MMA) polymerization was exemplified in the presence of CuBr/pentamethyldiethylenetriamine preparing i PP b-PMMA copolymers of different PMMA contents (c) 2010 Wiley Periodicals Inc J Polym Sci Part A Polym Chem 48 5783-5789 2010