Transition metal oxide semiconductors are attractive materials for hydrogen production by photo-induced water splitting. In this contribution, hematite (alpha-Fe2O3) films of different thickness grown over FTO conductive substrate, through spray pyrolysis method, were evaluated for water splitting under UV-vis irradiation using a Xe lamp. The films were characterized from X-ray diffraction, IR and UV-vis spectroscopic data. Their band gap (Eg), estimated from the recorded UV-vis spectra, and the photocurrent density (j), derived from the electrochemical data for water splitting, shown an inverse dependence on the film thickness. Such behavior is discussed according to the electron/hole mobility in the film. Copyright (C) 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.