A novel fibrous sulfated ZrO2 (SO42-/ZrO2) solid acid catalyst was prepared using collagen fiber as the template. The surface morphology of the as-prepared catalyst was observed by scanning electron microscopy (SEM), and the corresponding crystalline properties were determined by X-ray diffraction (XRD). To collect the structural properties of the SO42-/ZrO2 catalyst, N-2 adsorption/desorption method was carried out. Temperature-programmed decomposition (TPD) of ammonia was conducted to determine the acid strength of the catalyst. It was found that the SO42-/ZrO2 catalyst had well-defined fibrous morphology and porous structure, which contained both medium strong acidic sites and strong acidic sites. Subsequently, the esterification of acetic acid with n-butanol was carried out to evaluate the catalytic activity and reusability of the SO42-/ZrO2 catalyst. The SO42-/ZrO2 catalyst exhibited high catalytic activity as compared with other solid acid catalysts. Furthermore, the catalyst can be reused 6 times without significant loss of catalytic activity, suggesting a satisfied reusability. Crown Copyright (C) 2011 Published by Elsevier B.V. All rights reserved.