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 (ATRP), reversible addition–fragmentation transfer polymerization (RAFT), nitroxide-mediated polymerization (NMP), and degenerative transfer polymerization (DT). 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.