The present study shows the results obtained in the electrodeposition of hematite thin films from DMSO solution employing FeCl 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 α-Fe2O3 phase. XRD analyses confirm the presence of diffraction peaks corresponding to hematite after annealing, showing a strong preferential orientation of the  axis vertical to the substrate. Different techniques (XRD techniques, XPS analyses, SEM images, UV-Vis spectroscopy, Mott-Schottky plots and photocurrent-potential curves) have been employed in order to characterize the films and determinate their properties according with the conditions of electrodeposition and the annealing temperature.