Poly(vinyl alcohol) (PVA), PVA/Montmorillonite (MMT), PVA/Silver (Ag), and PVA/MMT/Ag nanocomposite nanowebs were prepared by electrospinning technique in aqueous solution. In order to investigate the effect of inorganic materials on the morphology and thermal properties of PVA based nanocomposite nanowebs, experiments were performed with 5 wt.% of MMT and Ag. Field emission type scanning electron microscopy, transmission electron microscopy (TEM), reflection type X-ray diffraction (XRD), and thermal gravimetric analyzer were utilized to characterize nanocomposite nanowebs. TEM and XRD results show MMT and Ag were well dispersed in PVA nanowebs. Those inorganic nanoparticles enhanced thermal property of the nanocomposite nanowebs.