Polymer nanofiber-supported perfluorosulfonic acid (PFSA)/SiO2 catalysts are successfully fabricated by electrospinning method from polymer/nanoparticle suspensions. This kind of catalyst has a large number of active acid sites and high specific surface area up to 85.6 m(2)/g. Scanning electron microscope images reveal that the catalysts present high porosity and inner-connected porous structure which varies much with SiO2 loading. Nitrogen adsorption-desorption measurements demonstrate a wide distribution of pore sizes inside the composites. Catalysts of different compositions are evaluated in esterification in a batch reactor under various conditions, and the results indicate that those of 20 wt % PFSA loading have the best activity of unit PFSA. Supporting PFSA by a nanofibrous matrix enhances liquid holdups inside the catalysts and offers accessibility of the acid sites, and therefore improves the activity of the catalysts. Moreover, these catalysts allow recovery at high percentages and regeneration with high activity.