Pt/SO42--ZrO2 catalysts (PSZ) were prepared by using a series of hydrous zirconia as support synthesized via a hydrothermal method. The catalytic performances of these catalysts were evaluated in the n-hexane isomerization in a fixed bed reactor. The crystalline structure, acidity, reduction properties, textural texture, and sulfur content were characterized by XRD, NH3-TPD, H2-TPR, N2 adsorption and thermal analysis. The experimental results indicated that the hydrothermal ageing of zirconium hydroxide led to great changes in the crystalline structure of hydrous zirconia support, sulfur content, and the acidity of PSZ. The abundant strong acid sites and high sulfur content were essential but insufficient to achieve a PSZ catalyst with high isomerization activity. Too weak or too strong interaction between sulfur species and zirconia in the catalysts was unfavorable to the isomerization reaction. The presence of considerable sulfate species interacting moderately with zirconia was crucial to high isomerization activity.