The stereospecific living radical polymerizations of methyl methacrylate (MMA) and 2-hydroxyethyl methaerylate (HEMA) were achieved with a combination of ruthenium-catalyzed living radical and solvent-mediated stereospecific radical polymerizations. Among a series of ruthenium complexes [RuCl2(PPh3)(3), Ru(Ind)Cl(PPh3)(2), and Ru.Cp*Cl(PPh3)(2)], Cp*-ruthenium afforded poly(methyl methacrylate) with highly controlled molecular weights [weight-average molecular weight/number-average molecular weight (M-w/M-n) = 1.08] and high syndiotacticity (r = 88%) in a fluoroalcohol such as (CF3)(2)C(Ph)OH at 0 degrees C. On the other hand, a hydroxy-functionalized monomer, HEMA, was polymerized with RuCp*Cl(PPh3)(2) in N,N-dimethylformamide and N,N-dimethylacetamide (DMA) to give syndiotactic polymers (r = 87-88%) with controlled molecular weights (M-w/M-n = 1.12-1.16). This was the first example of the syndiospecific living radical polymerization of HEMA. A fluoroalcohol [(CF3)(2)C(Ph)OH], which induced the syndiospecific radical polymerization of MMA, reduced the syndiospecificity in the HEMA polymerization to result in more or less atactic polymers (mm/mr/rr = 7.2/40.9/51.9%) with controlled molecular weights in the presence of RuCp*CI(PPh3)(2) at 80 degrees C. A successive living radical polymerization of HEMA in two solvents, first DMA followed by (CF3)(2)C(Ph)OH, resulted in stereoblock poly(2-hydroxyethyl methacrylate) with syndiotactic-atactic segments. (c) 2006 Wiley Periodicals, Inc.