Copolymerization of 1-octene and (meth)acrylates, such as methyl acrylate, trifluoroethyl acrylate (TFEA), methyl methacrylate, and trifluoroethyl methacrylate, under organotellurium-mediated living radical polymerization(TERP) conditions was investigated Polymerization under thermal conditions gave copolymers with considerably broad molecular distributions (polydispersity index [PDT] > 1.45), whereas that under photoirradiation greatly increased the PDI control. Structurally well-controlled copolymers with number-average molecular weights (M-n) of 3000-18 000 and low PDIs (1.22-1.45) Were obtained. Addition of Bronsted, acids, such as 1,3-C6H4[C(CF3)(2)OH](2) and hexafluoroisopropanol, increased the insertion of 1-octene into the copolymer. The molar fraction of 1-octene (MFoct) reached similar to 0.5 in the copolymerization using TFEA as an acrylate monomer and excess amount of 1-octene in the presence of the acid The copolymer was used as a Macro-chain-transfer agent for the synthesis of block copolymers. This is the first example of the use of this type of copolymer as a macro-chain-transfer agent in the controlled synthesis of block copolymers.