Sulfated zirconia catalysts were prepared by wetness impregnation of zirconium hydroxide with an aqueous solution of (NH4)2SO4 with SO42− loadings (1–30%, w/w) and calcined at 450 °C for 3 h in a static air atmosphere. The catalysts were characterized by FT-IR, XRD, TEM and BET measurements. The surface acidity of the catalysts was investigated by the dehydration of isopropanol and the adsorption of pyridine (PY) and 2,6-dimethyl pyridine (DMPY). The catalysts were tested for dehydration of methanol in a fixed-bed reactor at 230 °C using air as a carrier gas. The results revealed that among different catalysts, 10% SO42− supported onto zirconia showed the highest catalytic activity with 83% conversion and 100% selectivity toward dimethyl ether. A good correlation was found between the acidity of the catalysts and their ability to dehydrate methanol.