The electrochemical polymerization of o-toluidine has been investigated in oxalic acid solution. It was shown that the oxidation of monomer Could be achieved but this process does not yield a stable, homogenous polymer film on either platinum or mild steel electrodes. Therefore the copolymerization between pyrrole and o-toluidine has been studied as an alternative method for obtaining good quality coating (low permeability and water mobility, high stability), which could also be easily synthesized on steel. For this aim, various monomer feed ratio solutions of pyrrole:o-toluidine 9:1, 8:2 and 7:3 have been examined, in aqueous oxalic acid solution. By using cyclic voltammetry technique, copolymer films were realized on platinum and steel, successfully. The temperature of synthesis solution was found to have a vital role on polymerization and film growth, as much as the monomer feed ratio. The synthesis of homogenous copolymer film could only be achieved under <= 25 C conditions with using the 9:1 ratio, while the 8:2 ratios could only produce stable films below 5 C. As the amount of o-toludine increased the required temperature Value decreased further. 7:3 ratio Could only give a stable copolymer film below 2 C. The characterization of deposited copolymer coating has been realized by using SEM micrographs, UV-vis and FT-IR spectroscopy techniques and cyclic voltammetry. The protective behaviour of these coatings was also investigated against mild steel corrosion in 3.5% NaCl solution, by means of electrochemical impedance spectroscopy (EIS) and anodic polarization Curves. It was found that the monomer feed 8:2 ratio gave the most effective coating against the corrosion of mild steel. (C) 2008 Elsevier B.V. All rights reserved.