The oxidation of methanol at poly(Ni-II-tetramethyldibenzotetraaza[14] annulene) [Ni-II-(tmdbta)]-modified glassy carbon electrodes prepared by cyclic voltammetry are investigated by thin-film-electrode poly([Ni-II-(tmdbta)]) measurements. The poly([Ni-II-(tmdbta)])-modified electrode shows higher activity towards methanol oxidation in the Ni-III(tmdbta) state. The poly([Ni-II-(tmdbta)])-modified electrode is measured by cyclic voltammetry polarization curves and 8.5 h polarizations. The mechanisms of methanol oxidation are studied by cyclic voltammetry and polarization curves, and a reaction mechanism is proposed. The rate-determining steps are experimentally identified and the rate equation of methanol oxidation is obtained. The poly([Ni-II-(tmdbta)])-modified electrode remains stable during anodic polarization at 0.45 V for 8.5 h in 0.1 M NaOH solution with or without 0.1 M methanol. (C) 2004 Published by Elsevier Ltd.