Nickel hydrotalcites were subjected to synthesis using two methods: coprecipitation and urea hydrolysis. The thermal decomposition of the hydrotalcite precursors produced mixed oxides corresponding to the active phases or final catalysts. The precursors and the mixed oxides were characterized using atomic absorption spectroscopy (AA), X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), CO2 temperature-programmed desorption (TPD-CO2), textural properties, and temperature-programmed reduction with hydrogen (TPR-H-2). The catalysts were evaluated under conditions which simulate the autothermal reforming of ethanol toward the selective production of H-2. The solids synthesized via urea hydrolysis revealed the best reduction activity (higher hydrogen consumption at lower temperature) and larger average pore sizes, leading to better catalytic performance (higher H-2 selectivity). Superior catalytic performance is attributed to the production of smaller active phase particles, which are generated during the synthesis based on urea hydrolysis. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.