SO42-/TiO2-ZrO2 (STZ) solid superacid catalysts were prepared using the coprecipitation-impregnation method and characterized by FT-IR, XRD, NH3-TPD, N-2 adsorption-desorption isotherms, and SEM. It was observed that the sulfur content and the specific surface area of STZ changes with the ZrO2 content, and passes through a maximum at Zr/Ti = 1/4. The results indicate that the molar ratio of Zr/Ti and nonionic surfactant, PEG, were helpful for increasing the surface areas and stabilizing the sulfate species on the surfaces of the catalysts. The catalytic activity results were supported by the hydrolysis reaction rate of 2-methyl-1,3-dioxane (2MD) that was strongly dependent on the sulfur content in the zirconia promoted sulfated titania catalyst.