In the present work we demonstrate the usefulness of the palladized aluminum (A1/Pd) as a new electrode substrate for the electro-polymerization of phenylenediamines and fabrication of polymer film modified electrodes. The preparation and properties of poly(o-phenylenediamine) (PoPD), poly(m-phenylenediamine) (PmPD) and poly(p-phenylenediamine) (PpPD) film A1/Pd electrodes further modified with electrodeposition of platinum micro-particles were investigated by cyclic voltammetry. The electrooxidation of methanol was studied on the A1/Pd/Pt, A1/Pd/Pt covered by poly(phenylenediamines) (PPDA) and A1/Pd-modified by PPDA dispersed platinum electrodes in 0.1 M H2SO4 as supporting electrolyte. The effect of various factors such as amount of platinum incorporated, platinum incorporation method, thickness of the polymer films, concentration of methanol and medium temperature on the anodic current of methanol electrooxidation was studied and optimum value for each factor is suggested. A comparative study of permselective properties and platinum dispersion characteristic of PPDA films toward methanol has been performed. (c) 2006 Elsevier B.V. All rights reserved.