Abstract: A core-shell catalyst CuO-ZnO-Al₂O₃@Al₂O₃ for one-step synthesis of dimethyl ether from synthesis gas was prepared using glucose, sucrose or starch as template, and characterized by scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS). The thickness of the Al₂O₃ shell in the catalyst was altered by controlling the synthesis condition, such as temperature and time. The catalytic performance of dimethyl ether (DME) synthesized from CO hydrogenation on the catalysts were investigated. The conversion of CO and the selectivity of DME on CuO-ZnO-Al₂O₃@Al₂O₃ achieved 35.2% and 61.1% at 260 ℃, 5.0 MPa and 1 500 mL/(h·g_cat), respectively.