Ethanol steam reforming is an attracting process to produce hydrogen in a sustainable way. In this work the performance of Ni/TiO2 catalysts in ethanol steam reforming was studied. In particular, the effect of the synthesis procedure on the properties of the catalysts and on their activity was deeply investigated. On the basis of the experimental results, it was evidenced that TiO2-supported Ni systems are very sensitive to the synthesis parameters. We found that a proper thermal activation by calcination at 800 degrees C allows to obtain stable catalysts by means of strong interactions between the active phase and the support, preserving the catalyst from sintering phenomena. Nevertheless, the synthesis conditions must be properly tuned in order to prevent Ni incorporation in scarcely reducible structures which would depress catalytic activity. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.