To design efficient Cu-based catalysts for methanol-steam reforming (MSR) reaction, the Cu-Al-based layered double hydroxides (LDHs) substituted with Ni and Zn have been synthesized by the co-precipitation method. The prepared LDHs are calcined at 400 degrees C to form the mixed oxides and reduced at 250 degrees C for evaluating their catalytic performance, where water/methanol molar ratio and weight hourly space velocity (WHSV) are 1.1 and 12/h, respectively. These LDH-derived catalysts have also been characterized by XRD, TPR, N2O chemisorption analyses, etc. so that their physicochemical properties corresponding to their catalytic performances have been investigated. The experimental results and characterization data reveal that the reduced Cu-Al mixed oxide (Cu/Al molar ratio = 3) shows the best catalytic performance for MSR because the extremely high dispersion of Cu particles (CuO crystallite size < 10 nm) as well as the largest metallic surface area have successfully been achieved by the suggested preparation method despite of the highest Cu content. (C) 2016 Published by Elsevier Ltd on behalf of Hydrogen Energy Publications LLC.