Novel composite nanofibers consisting of Ag nanoparticles and polyacrylonitrile (PAN) were fabricated successfully. The Raman properties of these Ag/PAN nanofibers were studied at low temperatures, which showed good Raman characteristics. In the process, a PAN solutio containing Ag ions was directly electrospun to obtain nanofiber films containing Ag ions, and the Ag ions of resulting composite nanofibers were reduced to Ag nanoparticles in N2H5OH aqueous solution. Then, we treated Ag/PAN composite nanofibers at 100℃ , 200℃ , 400 and 600 ℃, respectively. The Ag/PAN nanocomposite film was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) patterns and surface-enhanced Raman scattering (SERS) spectroscopy.