A number of Fe-containing ZSM-5 zeolites, such as HFeZSM-5 and HFeAlZSM-5 prepared by hydrothermal synthesis and Fe-modified ZSM-5 through solid-state ion-exchange, were adopted as methanol dehydration catalysts for syngas to dimethyl ether (STD) process. Their structures, acidic and basic properties were characterized by XRD, ESR, ICP-AES, TPD and FT-IR. Among these Fe-containing zeolites, the Fe-modified ZSM-5 displayed the highest dimethyl ether selectivity, least CO 2 production. Some correlations between catalytic performance and acidity and basicity of Fe-containing ZSM-5 zeolite were discussed.