A novel fibrous catalyst containing palladium nanoparticles was produced via electrospinning technique. The fibrous catalyst was characterized by scanning electron microscopy and transmission electron microscopy respectively, the results show that the diameter of fiber was about 200 nm and the palladium (Pd) nanoparticles was in the range of 30-40 rim. The size and shape of Pd particles on the fiber can be adjusted by changing the concentration of polymer or amount of PdCl(2) in the electrospun solution. The catalyst was tested in hydrogenation of alpha-hexene and alpha-octene in ethanol at room temperature. The catalytic experimental results show that the activity of the titled catalyst was 4.7 times higher than that of PdCl(2)/gamma-Al(2)O(3) and higher than that of PdCl(2) on poly(styrene-divinyl benzene) resin catalyst (Zharmagambetov et al., J Mol Catal A: Chemical, 177, 165 (2001)). POLYM. COMPOS., 29:1346-1349, 2008. (C) 2008 Society of Plastics Engineers