Polyacrylonitrile nanofibers containing different amounts of gold nanoparticles have been prepared by electrospinning technique. By using the gold nanoparticles as seeds, thin continuous gold films have been deposited on the surface of polyacrylonitrile fibers through self-catalyzed reduction of chloroauric acid in solution. The conductivities of the fibrous mats increase with the amount of gold deposited on the fibers increase. The smooth continuous thin gold films tend to form on the fibers surface when the organic fibers contain more gold seeds, while coarse films tended to form on the fibers containing less gold seeds. The electrocatalytic activity of the fibrous mats electrodes towards the methanol oxidation in alkaline medium has been investigated, indicating that these electrodes exhibit higher electrocatalytic activity than pure gold electrode because of their three-dimensional structures. The results also indicate that the mats with smooth gold coating exhibit higher electrocatalytic activity than that with coarse gold coating. (C) 2008 Elsevier Ltd. All rights reserved.