Catalytic nanofibers are prepared by the immobilization of Au nanoparticles (AuNPs) onto the surface of cross-linked electrospun poly(4-vinylpyridine) (P4VP) nanofibers. The crosslinking of the P4VP nanofibers by 1,4-diiodobutane via quaternization reaction greatly enhances the stability of the nanofibers against the solvent dissolution, which can then be used as promising platform for the immobilization of catalytic metal nanoparticles. The AuNPs immobilized cross-linked P4VP nanofibers have shown a good catalytic activity for the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP).