A series of strong solid acids composed of WO3/ZrO2 were prepared. Their crystal structure, surface state, and acidity were determined by the methods of X-ray diffraction, thermal gravimetric and differential thermal analysis, temperature-programmed reduction, laser Raman, and acidity measurement. The results revealed that ZrO2 in WO3/ZrO2 existed mainly in the tetragonal phase, the addition of WO3 plays an important role in stabilizing the tetragonal phase of ZrO2, and all of the samples possessed large surface areas. WO3 in WO3/ZrO2 is mainly monolayer dispersed, and a small amount crystallized on the ZrO2 surface and partly reacted with ZrO2 to form the bond of Zr-O-W, acting as the strong solid acid center. The catalytic properties of WO3/ZrO2 strong solid;acids for alkylation of isobutane with butene at different conditions were investigated. They had a better reaction performance than other strong solid acids; a parallel relationship could be drawn between the catalytic activity and the acid amounts as well as the acidic strength of the catalysts.