SO2-4/ZrO2-SBA-15 catalyst was directly synthesized and characterized with XRD, BET and NH3-TPD. The results showed that this catalyst presents the typical mesoporous structure of SBA-15 and super acidity. This catalyst was used in the synthesis of ethyl tertiary butyl ether (ETBE) with ethanol and tert-butyl alcohol as raw materials on the fixed bed reactor. Its catalytic activity turns out superior to some other kinds of microporous zeolites, such as ZSM-5, USY and mordenite.