A series of mesoporous Cu-Ni-Al2O3-ZrO2 (XCNAZ) xerogel catalysts with different copper content (X, wt%) were prepared by a single-step epoxide-driven sol gel method, and they were applied to the hydrogen production by steam reforming of ethanol. All the calcined XCNAZ catalysts retained a mesoporous structure, and their surface area increased with increasing copper content. Metal-support interaction of XCNAZ catalysts decreased with increasing copper content due to the electronic effect. Nickel surface area and ethanol adsorption capacity of the catalysts exhibited volcano-shaped trends with respect to copper content. Among the catalysts, 0.2CNAZ catalyst exhibited the highest nickel surface area and the largest ethanol adsorption capacity. Catalytic performance in the steam reforming of ethanol over XCNAZ catalysts showed a volcano-shaped trend with respect to copper content. This result was well matched with the trend of nickel surface area. Thus, nickel surface area played a key role in determining the catalytic activity for steam reforming of ethanol. Among the catalysts tested, 0.2CNAZ catalyst with the highest nickel surface area (52.7 m(2)/g-Ni) showed the highest hydrogen yield (86.6%). That is, an optimal copper content was required for efficient hydrogen production by steam reforming of ethanol over XCNAZ catalysts. Copyright (C) 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.