The in-depth chemistry of a Ti/SnO2-Sb2O5 anode was investigated by X-ray photoelectron spectroscopy combined with ion etching. The coating was found to be composed of multiple layers of tin and titanium oxides and composition gradients at both the oxide-air and oxide-metal interfaces. The existence of such an extensive titanium oxide layer may be related to the fabrication of the Ti/SnO2-Sb2O5 anode and subsequent inter-diffusion of species. Also, the surface tin oxide layer was found to be non-stoichiometric, which, in relation to the extensive titanium oxide structure, could be explained by a migration of oxygen toward the Ti substrate. Electrochemical tests showed that the film was unstable and continued to grow under anodic polarization. Impedance spectroscopy displayed a continuum in the dielectric relaxation time constants with depth. This variation in relaxation time constants was proposed to be caused by the continuous variation of the composition in the film. (C) The Author(s) 2014. Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution Non-Commercial No Derivatives 4.0 License (CC BY-NC-ND, http://creativecommons.org/licenses/by-nc-nd/4.0/),which permits non-commercial reuse, distribution, and reproduction in any medium, provided the original work is not changed in any way and is properly cited. For permission for commercial reuse, please email: [email protected]. All rights reserved.