In this paper, iron oxide thin layers formed on mild steel substrates in alkaline media by the application of different anodic potentials were studied in order to characterize their morphology, composition and electrochemical behaviour, in particular under conditions of cathodic protection. The surface composition was evaluated by X-Ray Photoelectron Spectroscopy (xPS) and Auger Electron Spectroscopy (AES). The morphology of the surface oxides was studied via Atomic Force Microscopy (AFM). The electrochemical behaviour of the surface oxides was studied using Electrochemical impedance Spectroscopy (EIS). The results showed that the surface film is composed by Fe2+ oxides and Fe3+ oxides and/or hydroxides. The contribution of Fe2+ species vanishes when the potential of film formation increases in the passive domain. Two distinct phases were differentiated in the outer layers of the surface film, which proves that film growing is topotactic in nature. (C) 2008 Elsevier B.V. All rights reserved.