Well-formed poly (vinyl alcohol) (PVA)-perfluorinated sulfonic acid (PFSA) nanofiber mats were fabricated via electrospinning process. Homogenous PFSA-PVA solutions were prepared by mixing PFSA-N, N-dimethylacetamide (DMAc) solution with PVA aqueous solution at different weight ratio. Increasing the weight ratio of PFSA in solution greatly increased the viscosity of the solution and slightly decreased the conductivity, which increased the diameter of the resulting PVA-PFSA nanofiber. The operating parameters such as tip to collector distance (TCD) and flow rate have a limited effect on the morphology of nanofibers, but high flow rate can improve the productivity. Ethyl acetate synthesis catalyzed by PVA-PFSA nanofiber mats was investigated, the results showed that all nanofibers have significantly catalytic activity, but the catalytic efficiency is related to the specific surface of PVA-PFSA nanofibers. (C) 2011 Elsevier B.V. All rights reserved.