In this study, poly (vinyl alcohol) (PVA), lithium perchlorate (LiClO4) and nano-sized titanium oxide (TiO2) were employed as host polymer, dopant salt and inorganic filler respectively. The influence of the inorganic filler on ionic conductivity, structural and morphological properties of the polymer matrix are investigated. Ionic conductivity of polymer electrolytes is measured by ac-impedance spectroscopy at ambient temperature. The polymer electrolyte exhibits the highest ionic conductivity of 1.26×10 -4 S cm -1 upon addition of 8 wt. % TiO2. Dielectric behavior proves that incorporation of nano-sized TiO2 particles shows a significant effect on the dielectric constant of the polymer electrolyte system. XRD analyses disclose that the addition of TiO2 reduces the crystallinity of the polymer electrolytes which enhances the flexibility of polymer chains.