Bulk gamma-Fe2O3 (maghemite) and Fe3O4 (magnetite) were synthesized with Fe(III) hydroxyacetate as an intermediate during the preparation step. The fresh and used catalysts were characterized by X-ray diffraction, N-2 adsorption at 77 K, Mossbauer spectroscopy at 298 K, diffuse-reflectance spectroscopy, and thermogravimetric analysis. The solids were used as catalysts in the ethanol hydrotreatment within the range of 673-758 K. The catalysts showed a satisfactory selectivity for H-2 and an especially low CO production. These activities and selectivities were analyzed in conjunction with the structural properties of the oxides. Magnetite seemed to be a more appropriate catalyst than maghemite since the latter was converted into magnetite at reaction temperatures higher than 713 K because of the reducing atmosphere. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.