Copolymerization of acrylates, such as methyl acrylates (MAs) and trifluoroethyl acrylates (TFEAs), and 6-methyleneundecane (6MU), under organotellurium-mediated living radical polymerization (TERP) conditions, was investigated. Structurally well-controlled copolymers, poly(MA-co-6MU) and poly(TFEA-co-6MU), with predetermined number-average molecular weights (M-n = 3000-14000) and low polydispersity indices (PDI = 1.14 to 1.45) were obtained under thermal condition in the presence of an azo-initiator or photoirradiation. The addition of protic acids, such as 1,3-C6H4[C(CF3)(2)OH](2) and (CF3)(2)CHOH, was effective to increase the insertion of 6MU into the copolymer. The structure of the omega-polymer-end group was analyzed by using labeling experiments, which revealed that the majority of the end groups were derived from 6MU. Although activation of dormant species derived from alpha-olefin is difficult, the copolymers were successfully reactivated and served as macro-chain-transfer agents for the synthesis of block copolymers. Poly(MA-co-6MU)-block-styrene and poly(MA-co-6MU)-block-(N-vinylpyrrolidone) with controlled structures were synthesized for the first time.