Controlled random copolymerization of methyl acrylate (MA) with 1-alkenes was achieved through the reversible addition-fragmentation transfer (RAFT) technique using benzyl 1-pyrrol-carbodithioate as the transfer agent. NMR analysis reveals that RAFT agent-capped MA units are the predominant end groups. This allowed chain extension to synthesize the novel block copolymer, (MA-co-1-hexene)-b-PMA, by treating poly(MA-co-1-hexene) with AIBN in the presence of MA. The perfectly alternating copolymer of MA and ethene was obtained by using AlCl3 as the complexing agent. Additionally, the first controlled alternating copolymerization of MA and ethene was achieved by degenerative transfer polymerization with iodoform as transfer agent.