A series of CuO-ZnO-MO x (M = Zr, Al, Cr, Ti) catalysts were prepared by co-precipitation method and characterized by ICP-OES, XRD, N 2 adsorption, N 2 O titration, H 2 -TPR, and XPS. The CuO-ZnO-ZrO 2 catalyst exhibits the highest BET surface area and Cu surface area. For all the CuO-ZnO-MO x catalysts, Cu 0 was the predominant copper species detectable on the surface of both reduced and spent samples. As-prepared CuO-ZnO-MO x catalysts were mixed physically with HZSM-5 zeolite to synthesize dimethyl ether (DME) via biomass-derived syngas. The highest CO conversion and DME yield were obtained over a CuO-ZnO-ZrO 2 /HZSM-5 hybrid catalyst. The CO conversion increases with the increase in the Cu surface area, but the relationship between them is not linear. Due to the H 2 -deficient characteristic of biomass-derived syngas, the water-gas shift reaction, by which H 2 can be produced in-situ for the hydrogenation of CO, plays an important role in the direct DME synthesis. [ABSTRACT FROM AUTHOR]