A spark deposition process for the generation of crystalline titanium dioxide layers on barrier layer-forming metals such as Al, Ti, Mg, Zr, etc. was investigated. The process was carried out at high voltages and currents in an aqueous electrolyte. The electrolyte composition is provided and it could be shown that the electrolyte system used has great influence on the properties of the oxide layers. From the titanium balance, it was proven that most of the layer originates from the deposition of electrolyte compounds rather than from conversion of substrate material. Mechanistic conceptions of the layer formation are presented and supported by analytical determination of some reaction intermediates. The titanium dioxide layers generated were characterised regarding their physical and chemical properties. (C) 2004 Elsevier Ltd. All rights reserved.