In this research, new thin film of a free standing electrolyte film containing poly(vinyl) chloride (PVC), 50% liquid epoxidized natural rubber (LENR50), Ethylene carbonate (EC) blends as a host for the electrolyte which was doped with lithium perchlorate (LiClO<sub>4</sub>) as the dopant salt was successfully prepared with solution casting technique. The polymer electrolyte of PVC-LENR50-EC-LiClO<sub>4</sub> was characterized using impedance spectroscopy (EIS), scanning electron microscopy (SEM) and Fourier transform infrared (ATR-FTIR). From the EIS results shows that electrolyte exhibited the highest ionic conductivity of 2.1 × 10<sup>–7</sup> S●cm<sup>–1</sup> at the 30 wt.% of LiClO<sub>4</sub>. The ionic conductivity result was supported by the morphological studies which revealed the good homogeneity of the PVC-LENR50-EC blends as no phase separation was observed. The smooth surface can ease the mobility of ions in the system complexes. In addition, the formation of micro-pores by introducing lithium salts to the electrolyte also improved the transportation properties of L<sup>+</sup> ions in the electrolyte system and hence improving its ionic conductivity. The features of complexation of the electrolytes were studied by ATR-FTIR.
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