An attempt has been made to evaluate comparatively the behavior of 2-methylaniline (2MA) and 3-methylaniline (3MA) during electrochemical homo- and copolymerization. As comonomer in the copolymerization bath with 2MA and 3MA 1,2-diaminobenzene (1,2-DAB), an aromatic diamine, was selected. Cyclic voltammetry was used both for the electrochemical synthesis and characterization of the homopolymers and copolymers on a gold electrode. In the copolymerization bath mixed solutions of the monomers having different concentrations of 1,2-DAB and a constant concentration of 2MA or 3MA were used. The voltammograms exhibit different behavior for different concentration ratios of the monomer in the feed. The homopolymers poly(2-methylaniline) (P2MA) and poly(3-methylaniline) (P3MA) show similar electrochemical properties. However, differences were observed in the properties between the copolymers of 2MA and 3MA with 1,2-DAB that could be due to the variation in the monomer units and orientation along the copolymer chains. The copolymerization of 1,2-DAB seems to be more facilitated when instead of 3MA, 2MA is present as comonomers. The effect of scan rate and pH on the electrochemical activity was studied. The copolymers are surface confined, electroactive and show good electrochemical activity even at pH = 8.0 and pH = 9.0 in case of poly(1,2-DAB-co-3MA) and poly(1,2-DAB-co-2MA), respectively. In situ conductivity measurements further support the differences in the structure of the copolymers of 1,2-DAB with 2MA and 3MA. (C) 2012 Elsevier Ltd. All rights reserved.