Ni/Al2O3 catalysts containing 5 wt% of Ni and modified by addition of CaO (0-5 wt%) were tested in ethanol steam reforming reaction in order to reduce the dehydration ethanol reaction, which produces ethylene that may polymerize and produce coke. The catalysts were prepared by impregnation (I) and co-precipitation (C) methods. All catalysts were investigated for ethanol steam reforming and the catalytic performance was compared in terms of additive addition. The catalysts 5Ni-5Ca/Al (I) and 5Ni-5Ca/Al (C) were less selective to ethylene production and therefore were characterized by the following techniques: energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), temperature programmed reduction (TPR), X-ray absorption near edge structure (XANES), specific surface area by the BET method, scanning electron microcopy (SEM) and isopropanol decomposition reaction. By comparing the catalysts, the 5Ni-5Ca/Al (I) catalyst presented the lowest acidity and carbon deposition, and also presented no deactivation in 24 h of catalytic test. Copyright (c) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.