Polyaniline (PANI) films of different thickness have been deposited electrochemically at two different potentials of 0.8 and 1.2 V. Characterization of the surface composition of the material: oxidation states and structural changes have been performed using X-ray photoelectron spectroscopy (XPS). The main findings of this work show that the ratio of the imine to amine nitrogens for thicker films of PANI is close to unity, indicating that the surface layer of PANI is in the emeraldine form (base). On the other hand, the surface of thinner films of PANI contains similar to 14-20% imine nitrogen and similar to 60-70% amine nitrogen. This corresponds to an oxidation state close to that of protoemeraldine. Furthermore, XPS confirms a considerable amount of p-benzoquinone (BQ) as side product formed in all thin samples. The surface morphology examined by electron microscopy measurements shows that thin films have a uniform structure, whereas microporous structure with microchannels and microcaves inside, formed as a non-periodic network of microrods is characteristic for thicker PANI films. (C) 2008 Elsevier B.V. All rights reserved.