Catalytic oxidative polymerization of 2,2'-dihydroxybiphenyl (DHBP) was performed by using both the Schiff base monomer-Cu(II) complex and Schiff base polymer-Cu(II) complex compounds as catalysts and hydrogen peroxide as oxidant, respectively. The dependence of monomer conversion and molecular weight distribution on various reaction parameters, including time, temperature, solvent as well as the amount of catalyst and oxidant were investigated. The structure of the poly-2,2'-dihydroxybiphenyl (PDHBP) was confirmed by UV-vis, IR, H-1 and C-13 NMR spectroscopy techniques. The electrochemical and thermal properties of PDHBP were also studied. DSC data revealed that PDHBP was amorphous. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2977-2984, 2009