Supported catalysts are an increasingly popular research area because supported catalysts are highly efficient and the catalyst particles can be recovered. In this study, a new silica-supported palladium (Pd/SiO2) nanofiber catalyst was developed. Pd/SiO2 nanofibers were prepared by the electrospinning of a solution mixture of poly(vinyl pyrrolidone) (PVP), TEOS gel, and PdCl2 nanoparticles, followed by the calcination of PdCl2/PVP/TEOS nanofibers at a high temperature and the reduction of PdO/SiO2 nanofibers in a H-2 atmosphere. The results showed that the prepared Pd/SiO2 nanofibers had an average diameter of 500 nm. Pd nanoparticles with a diameter of 20-30 nm were uniformly dispersed on the surface of SiO2 nanofibers. The composite nanofibers had high Brunauer-Emmett-Teller (BET) specific surface area. The hydrogenation reaction for acrylic acid showed that the hydrogenation efficiency was 93.48% in the presence of 0.1 g of Pd/SiO2 nanofibers. These nanofibers could be easily recycled. These features make the Pd/SiO2 nanofibers promising in a wide range of applications in the catalyst industry.