The present invention is directed to methods of making a nanofiber-nanoparticle network to be used as electrodes of fuel cells. The method comprises electrospinning a polymer-containing material on a substrate to form nanofibers and electrospraying a catalyst-containing material on the nanofibers on the same substrate. The nanofiber-nanoparticle network made by the methods is suitable for use as electrodes in fuel cells.