The ultrafine polymethylmethacrylate fibers containing gold nanoparticles have been prepared by using the electrospinning technique. Then the continuously coarse gold films formed by fractal-like thorny gold particles were deposited on the organic eletrospun fiber surface by an electroless process. The morphology of coarse gold films was characterized by scanning electron and transmission electron microscopy. The results revealed that the morphology of the gold particles was affected not only by the amount of gold seeds embedded in the organic fibers but also by the amount of gold deposited on the fiber's surfaces. The surface-enhanced Raman scattering (SERS) effect of the fibrous mats coated with gold films was evaluated by using Rhodamine B as an adsorbate. The results indicated that this kind of fibrous mat exhibited high and reproducible SERS activity and could be developed as highly sensitive SERS substrate. (C) 2009 Elsevier B.V. All rights reserved.