Herein we report an effective method for the preparation of composite nanofibers of polybutadiene rubber (BR) containing uniformly distributed Ag nanoparticles (Ag NPs). These nanofibers were morphologically stable and were made from electrospun core-sheath nanofibers with the sheath component being polyvinyl pyrrolidone (PVP) and the core component being BR, in situ synthesized Ag NPs, and a photo-curing agent of camphorquinone. The method included (1) co-axial electrospinning of core-sheath nanofibers, (2) in situ chemical crosslinking of BR in the core component of nanofibers, and (3) removal of the sheath component of PVP from nanofibers. The experimental observation indicated that, when the flow rate of inner spin dope was slower than that of the outer spin dope, the co-axial electrospinning process would be stable, the resulting nanofibers would not be curled; and there were few conglutination locations among the core-sheath nanofibers. Both electrospun core-sheath nanofibers and the resulting composite nanofibers possessed the cylindrical morphology with smooth surface. The study also revealed that the Ag in the composite nanofibers primarily existed in the elemental form. (C) 2012 Elsevier B.V. All rights reserved.