A series of CuO-ZnO-Al2O3-Li2O catalysts with various Al2O3-Li2O mass ratios were prepared by co precipitation method and characterized by several techniques such as XRD, N-2 adsorption, SEM/EDX, reactive N2O adsorption, XPS/XAES, H-2-TPR, H-2-TPD, and CO-TPD. The results revealed that the specific surface area (SBET), dispersity of Cu species, metallic Cu surface area (Sc) and adsorption capacity for reactants (H-2 and CO) were increased by the addition of suitable amount of Li2O to the CuO-ZnO-Al2O3 catalyst, thus enhancing the catalytic activity of the hybrid catalyst composed of CuO-ZnO-Al2O3 and HZSM-5 for the direct synthesis of dimethyl ether from biomass-derived gas. Furthermore, the addition of Li2O significantly improved the stability of CuO-ZnO-Al2O3 catalyst due to the effective inhibition of the crystallization of Cu and ZnO. (C) 2017 Elsevier Ltd. All rights reserved.