Electrochemical experiments on titanium electrodes were coupled with electron backscatteied diffraction (EBSD) experiments. The substrates were thermally treated and electropolished in order to have flat and reproducible polycrystalline surfaces, leading to EBSD orientation mapping. Afterwards, the samples were anodised by a galvanostatic procedure. It was shown that electrodeposition of PbO2 from a 0.5 M Pb(NO3)(2) + 2.5 M HNO3 solution occurs selectively on the near {0 0 0 1} grains, whereas lead electrodeposition occurs on all the grains, whatever their orientation. These results are discussed, taking into account the fact that on {0 0 0 1} grains, the oxide layers are thinner than on other grains. It was concluded that electrodeposition is observed locally on Ti/TiO2 electrodes for (i) cathodic electrodeposition of metals at low overvoltage; (ii) anodic electrodeposition of PbO2, in potentiostatic or galvanostatic conditions. (C) 2004 Elsevier Ltd. All rights reserved.