In this paper, nanotubular arrays of TiO2 are used as anode in an undivided electrochemical cell where the water photosplitting process may occur enhanced by the external applied potential. The behavior of the nanotubular structure, prepared by electrochemical anodization of Ti foils, is investigated. All the samples were submitted to thermal annealing in order to transform the amorphous structure into crystalline. Emphasis is paid on the influence of the current transient during the anodization on the photochemical response of the samples. Depending on the current transient, a different distribution of defects, at the surface or in the bulk, is originated in the initial structure, which resulted differently sensitive to the temperature. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.