A highly active manganese complex [Mn-2(CO)(10)] efficiently induced the controlled/living radical copolymerizations of a conjugated polar vinyl monomer, methyl acrylate (MA), and an unconjugated nonpolar olefin, 1-hexene (1-Hex), in the presence of ethyl 2-iodoisobutyrate (EMA-I) as an initiator under weak visible light at 40 degrees C to give the copolymers with controlled molecular weights. The further use of protic fluoroalcohols as solvents enhanced the copolymerization without losing the molecular weight control to result in a high I-Hex content LIP to 50 mol %, for which the predominant alternating sequences were confirmed by the C-13 NMR analysis of the copolymers. The kinetic analysis of the copolymerizations revealed an increase in the reactivity of the MA-radical to the 1-Hex monomer in the fluoroalcohol [1/r(MA) = 0.49 in (CF3)(2)CHOH vs 0.081 in toluene], which can be attributed to the 1:1 hydrogen-bonding interaction between the MA unit and the fluoroalcohol as suggested by the C-13 NMR analysis of the MA-fluoroalcohol mixtures [K-assn = = 2.21 L/mol for (CF3)(2)CHOH]. Thus, a combination of a highly active Mn-2(CO)(10) catalyst and a protic fluoroalcohol solvent is effective for the alternating controlled/living radical copolymerization of acrylic monomers and alpha-olefins.