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ZrO2 was treated with 10％ SO2-4 from different metal sulfate precursors for methanol dehydration to dimethyl ether. All the samples exhibited tetragonal phase and no diffraction peaks corresponding to metal sulfates or metal oxides were observed. The FT-IR results revealed that there were different interactions between sulfate and ZrO2 , and this had a great effect on the surface area of the samples. The catalytic activity was measured over the catalysts in the temperature range of 100-300℃. The results revealed that sulfated zirconia with CuSO4·5H2O and Al2(SO4)3·16H2O showed the best catalytic activity. The maximum yield of DME≈87％ was obtained over CuSZ at a reaction temperature of 275℃. Moreover, the catalytic activity of the catalysts was correlated well with their surface acidity that measured by dehydration of isopropanol.