A new method for ethanol synthesis from dimethyl ether (DME) and syngas via a two-stage reaction system was established successfully. In the first stage reaction, H-mordenite zeolite catalyst was used to convert DME into methyl acetate (MA) through carbonylation reaction. The MA produced from the first stage reactor was hydrogenated by Cu/ZnO catalyst in the followed second stage reactor to form ethanol and methanol. The effect of the variation of various metal-supported zeolites on the products distribution for each stage reaction was investigated.