Present paper reports a method of preparing polymer composite electrolyte nanofiber mat using polyvinyl alcohol (PVA), ammonium thiocynate (NH4SCN) salt, and aluminium oxide (Al2O3) nano particles based on electrospinning technique. Two-stage process of preparation of nanofibers, namely, preparation of nano particles filled PVA electrolyte gel solution followed by its electrospinning has been used. The so obtained nanofibers have been characterized by XRD, DSC, SEM, and Conductivity measurements. XRD patterns affirm the formation of nanocomposite while SEM pictures reveal formation of fibers on a nano scale format (300-800 nm). Fibers of the electrolytes are seen to be thermally stable. Ionic conductivity of electrolyte fiber is seen to improve in the presence of nano filler at room temperature with a maximum at 5.31x10(-3)Scm(-1) for 4 wt% filler concentration, which is comparable to that for corresponding dried gel electrolyte films.