The electrochemical synthesis of poly(o-phenylenediamine) (PoPD) from an aqueous medium was suitably modified by controlling the switching potential to enhance the growth of the polymer. The charge-discharge data for the cell Zn/1 M ZnSO4 (pH 4)/PoPD are presented. The polymer was modified by incorporating Pt microparticles into its matrix during electropolymerization. The PoPD-Pt composite electrode was also characterized as a cathode active material in aqueous cells.