A WC-supported S2O2-8/ZrO2(PSZ) catalyst was prepared and characterized by means of XRD, BET, FTIR and XPS. The isomerization of n-pentane over the catalyst was investigated as well. The results show that the skeletal isomerization and the crack of n-pentane proceed simultaneously on WC-supported S2O2-8/ZrO2 catalyst. The addition of tungsten carbide showed a significant enhancement in the activity and stability of the catalyst for n-pentane isomerization. The catalyst showed evidently a better activity than S2O2-8/ZrO2 supported by Pt and WO3. The results can be interpreted by the existence of the tungsten oxycarbide compound(WCxOy) with carbidic, oxide and acidic sites.