The new plasticised polymer electrolyte comprising the blend of poly-vinyl chloride (PVC) and poly-methylmethacrylate (PMMA) as host polymer is preferable to classical polymer for improving the ionic conductivity in the lithium rechargeable batteries. The nature of plasticizer and Lithium salts have been found to influence the ionic conduction of the polymer-blended electrolytes. AC impedance analysis revealed the choice available in imparting ionic conductivity while differential thermogravimetry (DTG) and FTIR analysis have facilitated the effect of molecular interaction on host polymer matrix.