High performance copper-based catalysts (CuNiZnO/gamma-Al2O3) for hydrogen production from methanol decomposition were successfully synthesized by the method of microwave-assisted thermal hydrolysis of urea. The ICP-OES, N-2 adsorption-desorption, SEM, TEM, XRD and H-2-TPR were applied to characterize the physicochemical properties of the prepared materials. These experiment results reveal that the higher thermal treatment temperature can improve the catalytic performance by enlarging the content of promoters (Zn and Ni) and promoting the dispersion of deposited particles. Moreover, the addition of Ni can significantly improve the catalytic performance of the copper-based catalysts, which is ascribed to the regulation of reaction process and inhibition of Cu-Zn alloy. Among the obtained catalysts, the MW-Cu/Ni-95 developed at 95 degrees C exhibits a higher catalytic activity, which reaches 91.7% conversion at 250 degrees C. Most significantly, it shows the excellent catalytic performance as compared with the commercial catalyst under the same test conditions. (C) 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.