Syndiotactic poly(methacrylic acid) (Syn-PMAA, r diad = 91 mol %) was synthesized by free radical polymerization of methacrylic acid (MAA) with catechol. The pseudo-divinyl monomer was formed with one catechol and two MAA molecules by the hydrogen bonding between OH groups of catechol and COOH group of MAA. When the free radical polymerization of the pseudo-divinyl monomer was carried out, intra- and intermolecular addition proceeded with racemic addition. The hydrogen bonding was the driving force to control tacticity. We discussed the effects of solvent, temperature, and the concentrations of MAA and catechol on the pseudo-divinyl monomer formation. The highly syndiotactic PMAA was successfully obtained. (c) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013