Synthesized wurtzite ZnO nanostructures are incorporated on the poly (vinylidenefluoride-co-hexafluoropropylene) (PVdF- co -HFP) matrix, which improves the thermal behavior of as obtained thin film nanocomposite microporous polymer membrane (nanoCMPM). The nanoCMPM shows a favorable effect on the melting temperature (T m ) 142.9°C. The nanocomposite membranes were characterized by DSC and porosity studies. The nanoCMPM was prepared as a polymer electrolyte in soaking 1.0 M LiClO 4 – DMC+EC (1: 1 v/v ratio) electrolyte solution to get as nanocomposite polymer electrolytes (nanoCMPE). The optimized nanofiller dispersed composite microporous polymer membrane was found to have a high degree of porosity (76%) and excellent film strength than 8-10wt% filler concentration. It shows the ionic conductivity in the order of 10 −3 S cm −1 at room temperature. It has been further evidence from the effect on lithium salt concentration studies. The optimized membrane electrolyte has good compatibility and charge discharge character at 0.5C rate. It has the evidence applicable to perform in lithium ion polymer batteries.