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A novel polymer nano composite electrolyte composed of PVA polymer matrix with ZrO 2 ceramic filler and NaClO 4 salt was prepared by a solution casting. The characteristic properties of PVA/NaClO 4 polymer composite electrolytes with ZrO 2 filler were studied using FTIR, X-ray diffractometer (XRD), FESEM, DSC, AFM, AC impedance method, and cyclic voltammeter. The sample containing 3 wt% ZrO 2 exhibits good mechanical strength, high conductivity, high dielectric constant and good electrochemical response at room temperature. The conduction mechanism of the composite can be represented by the correlated barrier hopping (CBH) model and the obtained frequency dependent S parameter obeys Almond-West Universal power law. Using Williams-Landel-Ferry (WLF) and Vogel Fulcher Tamman (VTF) equations equivalence correlated the dynamic fragility (m) and activation energy (E g ) with T g of polymer composites. Transport parameters were calculated using Rice and Roth model. The cyclic voltamograms shows that the prepared films were Pseudo-capacitive in nature. POLYM. COMPOS., 00:000-000, 2016.