In This work, Silver nanoparticles were synthesized via a simple chemical reaction. For the production of Ag nanoparticles (NPs), starch was used as a surface-active agent. Poly vinyl alcohol (PVA) nanofibers and their nanocomposites with Ag nanoparticles were prepared by electrospinning method. The structures and morphologies of the prepared samples were investigated by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and thermos-gravimetric analysis (TGA). Nontoxic nanoparticles appropriately enhanced both thermal stability and flame retardant property of the PVA matrix.