The living/controlled copolymerization of methyl acrylate with 1-alkenes and norbornene derivatives through several radical polymerization techniques has been achieved. These techniques include atom transfer radical polymerization, reversible addition-fragmentation transfer polymerization, nitroxide-mediated polymerization, and degenerative transfer polymerization. These systems display many of the characteristics of a living polymerization process: the molecular weight increases linearly with the overall conversion, but the polydispersity remains low. Novel block copolymers have been synthesized through the sequential addition of monomers or chain extension. (C) 2004 Wiley Periodicals, Inc.