The catalyst was prepared with HZSM-5 as support and ammonium sulfate as modifying agent by impregnation, filtration, desiccation and calcinations. The ethylene glycol monoethyl ether and ethylene glycol diethyl ether were synthesized from ethylene glycol and ethanol by using prepared catalysts. The results showed that modified H-ZSM-5 was the better catalyst. The conversation of ethylene glycol was 69.1% and the selectivity of ethylene glycol monoethyl ether was 72.9% and selectivity of ethylene glycol diethyl ether was 25.3%. However, the catalytic performance dropped after be used. And so the catalyst samples were characterized by X-ray diffraction (XRD), temperature-programmed desorption of NH3 (NH3-TPD), scanning electron microscopy (SEM) with the energy dispersive spectroscopy (EDS), Brunner-Emmit-Teller (BET) and thermogravimetry (TG) to investigate the deactivation of the catalyst. The results showed that the catalyst deactivation did not result from the change of the crystal structure. The main reason for catalyst deactivation is the reduced of sulfur and strong acid sites because of the absorption of organic molecules on the surface or in the pore of the catalyst.