In this paper, thin surface films were formed on AISI 316 immersed in alkaline solutions of pH ranging from 13 to 9 under open circuit potential conditions. The electrochemical behaviour of the films formed under these conditions was evaluated by different electrochemical techniques: d.c. potentiodynamic polarisation, capacitance measurements (Mott-Schottky approach) and electrochemical impedance spectroscopy. The chemical composition was studied by X-ray photoelectron spectroscopy (XPS). The results reveal a good agreement between the film composition, the electronic properties and the electrochemical behaviour. The analytical results showed that the composition of the surface film changes with the pH. The films become enriched in Cr(III) and Fe(III) species and depleted in Fe(II) and Ni species, as the pH decreases from 13 to 9. The results are consistent with the formation of a film, presenting a bilayer structure, composed of an outer oxide/hydroxide layer, enriched in iron, and an inner anhydrous layer, rich in chromium and nickel oxides. Impedance measurements reveal that the resistance of the surface film increases during immersion and that the pH influences the evolution of the charge transfer resistance and the evolution of the film capacitance. Capacitance measurements based on the Mott-Schottky approach show that the concentration of electronic defects decreases with pH and that the films formed at pH 13 present the highest density of donors and, therefore, a more conductive behaviour. (C) 2009 Elsevier Ltd. All rights reserved.