Iron-supported HZSM-5 catalysts were prepared by hydrothermal (Fe-HZSM-5_HYD) and impregnation methods (Fe/HZSM-5_IMP). The active species of binuclear-iron complex and iron-substituted zeolite framework, confirmed by EXAFS analysis, were observed on Fe/HZSM-5_IMP and Fe-HZSM-5_HYD, respectively. The catalysts were used for production of dimethyl ether (DME) by methanol dehydration at 200-350 °C using fixed bed flow reactor. Fe/HZSM-5_IMP showed higher catalytic conversion than Fe-HZSM-5_HYD. However, the Fe/HZSM-5_IMP catalyst was less selective to DME product and strongly deactivated for 24h. The deactivation might due to transformation of binuclear-iron to the a-iron site which was strong acidic strengh. The iron-substituted zeolite framework of Fe-HZSM-5_HYD showed high stability toward methanol dehydration. Moreover, the catalyst showed advantages of good selective to DME and low carbon deposition on surface. These results suggested that the iron-substituted zeolite framework structure could improve catalytic performance for mrthanol dehydration.