In the present study, continuous and uniform core-shell silver nanofiber/poly(vinyl) pyrrolidone (AgNF/PVP) nanofibers have been successfully fabricated via an efficient coaxial-spinneret electrospinning method with a vertical configuration using PVP and AgNO3 as precursor solutions. PVP polymer was primarily used as a guide and provided an appropriate viscoelastic property by surrounding the AgNO3 (core) solution to fabricate aligned AgNF/PVP core-shell nanofibers. A series of AgNO3 concentrations were prepared by fixing the concentration of PVP as the shell fluid. The AgNO3 concentration had a significant influence on the formation of the continuous and uniform AgNF/PVP core-shell nanofiber structure and applied voltage had an effect on the formation of the compound stable Taylor cone. The (AgNF/PVP) core-shell nanofibers were formed via the stretching of the co-electrospinning jet and the reduction temperature for an appropriate time induced the silver nanofiber to be well aligned along the axis of the PVPtemplate electrospun fiber. The structure and properties of the thus obtained core-shell nanofibers were investigated thoroughly through optical microscopy (OM), transmission electron microscopy (TEM), focused ion beam (FIB), X-ray diffraction (XRD) and selected area electron diffraction (SAED). Energy dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) were also employed to analyze the elemental composition of the core-shell nanofiber surface. On the other hand, UV-vis spectrophotometry was used to test the reduction of silver ions into metal silver. Moreover, electrical measurements were performed on the (AgNF/PVP) core-shell nanofibers, which indicated that the core-shell nanofibers became insulating due to the embedded highly conductive silver nanofibers by insulating the PVP shell. Therefore, coaxial electrospinning is a convenient and cost effective process for the fabrication of continuous and uniform (metal/polymer) core-shell nanostructure fibers.