Plasticized polymer electrolyte comprising poly (vinylidene fluoride-co-hexa fluoro propylene), poly (methyl methacrylate), and Lithium per chlorate as the complexing salt with different concentrations of Propylene carbonate has been prepared exhibiting an ionic conductivity of the order of 10-3 S cm-1. Temperature dependent ionic conductivity seems to obey Vogel Tamman Fulcher relation, and the transport mechanism has been discussed on the basis of free volume theory. The structural elucidations have been ascertained from X-ray diffraction and Fourier transform infrared spectroscopy. Thermal stability of the electrolyte has been asserted based on results from Differential Scanning Calorimetry.