The synthesis of dimethyl ether (DME) from a model gas mixture of biomass-derived syngas has been investigated on the composite catalysts, Cu–ZnO–Al2O3/Zr-modified zeolites (Ferrierite, ZSM-5 and Y). The composite catalysts were synthesized by the coprecipitation of Cu–Zn–Al precursors in the slurry of Zr-modified zeolites. The composite catalyst prepared from Zr–ferrierite showed stable activity and the best DME selectivity. Apart from the easy reducibility of Cu species, the presence of appropriate acid sites of required strength for methanol dehydration is proposed to be the reason for the superior performance of Cu–ZnO–Al2O3/Zr–Ferrierite catalyst.