The results of an experimental study on the photo electrochemical behavior of nanotubular TiO2 structures are presented in this work. TiO2 samples were prepared by electrochemical anodization of Ti foils and submitted to thermal annealing. The influence of the current transient during the anodization, and of the annealing temperature on the photochemical response of the samples at different wavelengths was studied. Different behavior of the samples was observed, which may be attributed to the distributions of defects and to their different sensitivity to the temperature. The analysis of the performance of the samples in absence or in the presence of glycerol, used as hole scavenger, provided more information on the photo-catalytic properties of these structures.