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　°C　for　5　h　has　the　highest　catalytic　activity.