This paper focuses on the characterisation of the electrochemical behaviour of a martensitic stainless steel in 0.1 M NaCl + 0.04 M Na2SO4 solution and is a part of a study devoted to crevice corrosion resistance of stainless steels. Polarisation curves and electrochemical impedance measurements were obtained for different experimental conditions in bulk electrolyte. X-ray photoelectron spectroscopy (XPS) was used to analyse the passive films. At the corrosion potential, the stainless steel was in the passive state and the corrosion process was controlled by the properties of the passive film formed during air exposure. During immersion in the deaerated solution, the passive film was only slightly modified, whereas it was altered both in composition and thickness during immersion in the aerated solution, After cathodic polarisation of the stainless steel electrode surface, the oxide film was almost totally removed and the surface appeared to be uniformly active for oxygen reduction. The new passive film, formed at the corrosion potential, was enriched with iron species and less protective. Impedance diagrams allowed the characterisation of both the oxide film (high-frequency range) and the charge transfer process (low-frequency range). (C) 2012 Elsevier Ltd. All rights reserved.