Several preparation methods of WO3/ZrO2 solid superacid catalysts were introduced. The effects of preparation conditions on characteristic properties of WO3/ZrO2 and on catalytic performance of alkane isomerization were summarized. Research progress of alkane isomerization catalyzed by WO3/ZrO2 and modified WO3/ZrO2 was reviewed in detail. It is confirmed by researchers that these catalysts had a high catalytic activity to alkane isomerization, and the content of WO3, calcination temperature and the crystal form of ZrO2 were the main influencing factors of catalytic performance for alkane isomerization. Surface structure of WO3/ZrO2 was briefly discussed, and the research emphasis of WO3/ZrO2 solid superacid catalyst in the future was also predicted.