The behaviour of TiO2 based electrodes was investigated during the photoelectrocatalytic water splitting process. TiO2 nanotubes and compact oxide structures were obtained by electrochemical oxidation of Ti foils. A subsequent hydrothermal process carried out at both the nanotubular and compact oxide structures allowed decorating the structure by TiO2 nanoparticles. The synthesized TiO2 samples worked as photoanodes both in a bulk three electrode cell and in a thin gap cell. The results from measurements of the photocurrent and from electrochemical impedance spectroscopy were used to highlight a combined effect of the wavelength of the incident light and the kind of cell configuration, on the global performance of the systems. The results indicate that the decoration process does not result only in a simple increase of the specific surface, but it also determines a different concentration of the bulk and superficial sites in the electrode. The different response of the sites at different wavelengths, along with the accessibility of the electrolyte to the porous structure are evocated to justify the experimental behaviour observed
