The present study shows the results obtained in the electrodeposition of hematite thin films from DMSO solution employing FeCl3 and molecular oxygen as precursors. The films were obtained through a potential cycling program at different cathodic limits and at different electrolytic bath temperatures. In all cases, as-grown films were amorphous and photoelectrochemically inactive. An annealing procedure is necessary to completely transform the electrodeposited iron oxide to the alpha-Fe2O3 phase. XRD analyzes confirm the presence of diffraction peaks corresponding to hematite after annealing, showing a strong preferential orientation of the [110] axis vertical to the substrate. Different techniques (XRD, XPS, SEM, UV-Vis spectroscopy, Mott-Schottky plots and photocurrent - potential curves) have been employed in order to characterize the films and determine their properties as a function of the conditions of electrodeposition and the annealing temperature. (C) 2014 The Electrochemical Society. All rights reserved.