Characterizations were carried out to study on a new plasticized solid polymer electrolyte that was composed of blends of poly(vinyl chloride) (PVC), liquid 50% epoxidized natural rubber (LENR50), ethylene carbonate, and polypropylene carbonate. This freestanding solid polymer electrolyte (SPE) was successfully prepared by solution casting technique. Further analysis and characterizations were carried out by using scanning electron microscopy (SEM), X-ray diffraction, differential scanning calorimeter (DSC), Fourier transform infrared (ATR-FTIR), and impedance spectroscopy (EIS). The SEM results show that the morphologies of SPEs are compatible with good homogeneity. No agglomeration was observed. However, upon addition of salt, formation of micropores occurred. It is worth to note that micropores improve the mobility of ions in the SPE system, thus increased the ionic conductivity whereas the crystallinity analysis for SPEs indicates that the LiClO 4 salt is well complexed in the plasticized PVC-LENR50 as no sharp crystallinity peak was observed for 5-15% wt. LiClO 4 . This implies that LiClO 4 salt interacts with polymer host as more bonds are form via coordination bonding. In DSC study, it is found that the glass temperature (T g ) increased with the concentration of LiClO 4 . The lowest T g was obtained at 41.6°C when incorporated with 15% wt. LiClO 4 . The features of complexation in the electrolyte matrix were studied using ATR-FTIR at the peaks of C0O, C-O-C, and C-Cl. In EIS analysis, the highest ionic conductivity obtained was 1.20× 10 −3 S cm −1 at 15% wt. LiClO 4 at 353 K.