The AgNO3/polyacrylonitrile hybrid nanofibers were prepared by using electrospinning technique, then the hybrid fibers of AgNO3/polyacrylonitrile were treated with pyrrole in the boiling toluene medium, finally, the silver/polypyrrole/polyacrylonitrile composite fibrous mats were obtained. The scanning electron microscopy, transmission electron microscopy, X-ray diffraction and Raman spectra were used to characterize the obtained silver/polypyrrole/polyacrylonitrile composite fibrous mats. And the results indicated that the morphologies of the composite fibers were influenced by the content of AgNO3 in the AgNO3/polyacrylonitrile fibers. The silver/polypyrrole composite dispersed in the fibrous mats exhibited core-shell structure, and the conductivity of the optimum silver/polypyrrole/polyacrylonitrile composite fibrous mats is relatively high. (C) 2008 Elsevier B.V. All rights reserved.