Abstract: WO₃/ZrO₂ solid acid catalyst with hierarchically porous structure was prepared by the one-pot hydrothermal method involving templating from a composite surfactant. The catalyst samples were characterized by X-ray diffraction, N₂ adsorption-desorption, Raman spectroscopy and NH₃ temperature-programmed desorption. The results indicated that WO₃ doping significantly increased the BET surface area and provided more surface acid centers. The esterification of acetic acid and butanol showed that the hierarchically porous WO₃/ZrO₂ solid acid catalyst has excellent catalytic activity and reusability. The 20% WO₃/ZrO₂ sample calcined at 550 ^oC for 5 h has the highest catalytic activity.

Key words: tungsten oxide, zirconia, hierarchical pore, solid superacid, acetic acid, n-butanol, esterification, butyl acetate, reusability