Electropolymerized films of teraaminometallophthalocyanines (MTAPc; M = Ni and Co) with amino groups at alpha-(4 alpha-MTAPc) and beta-(4 beta-MTAPc) positions were prepared on glassy carbon (GC) and indium tin oxide (ITO) electrodes. It was found that the electropolymerization growth rate of 4 alpha-MTAPc was less than that of 4 beta-MTAPc prepared under identical conditions. Further, the surface coverage of the polymerized 4 beta-MTAPc film was greater than that of 4 alpha-MTAPc polymerized film. Atomic force microscopy (AFM), X-ray diffraction (XRD) and UV-visible spectroscopic studies were carried out for the polymerized films of 4 alpha-Ni(II)TAPc(p-4 alpha-Ni(II)TAPc) and 4 beta-Ni(II)TAPc(p-4 beta-Ni(II)TAPc) alone because both Ni(II) and Co(II) polymerized films show similar trend in electropolymerization and surface coverage values. AFM images show that p-4 alpha-Ni(II)TAPc film contains islands and the thickness of this film was nearly three times less than that of p-4 beta-Ni(II)TAPc. XRD patterns for the two polymerized films reveal that p-4 beta-Ni(II)TAPc film was relatively more crystalline than p-4 alpha-Ni(II)TAPc film. Further, the compactness of these films was scrutinized from their barrier properties toward [Fe(CN)(6)](3-/4-) redox couple. The differences in the polymerization growth rate of 4a-MTAPc and 4 beta-MTAPc, and the thicknesses of the resultant polymerized films suggest that unlike 4 beta-MTAPc one or two amino groups might have not involved in electropolymerization in the case of 4 alpha-MTAPc. Further, the influence of surface coverage on the electrocatalytic properties of the polymerized films was studied by taking p-4 beta-Co(II)TAPc and p-4 alpha-Co(II)TAPc films as examples. The electrocatalytic oxygen reduction current was almost same at both the electrodes suggesting that only the surface species were involved in the electrocatalytic reduction of oxygen. (C) 2008 Elsevier Ltd. All rights reserved.