Plasticized poly(vinyl chloride)/poly(ethyl methacrylate) PVC/PEMA-based blend polymer electrolyte films containing lithium perchlorate (LiClO4) as a salt were prepared by solvent casting technique. The effects of the plasticization on structural, thermal and electrical properties of the plasticized polymer blend electrolytes were investigated. The changes in the structural and complex formation properties of the materials were studied by XRD and FTIR techniques. Dielectric relaxation studies of the polymer electrolyte have been undertaken, and the results are discussed. TG/DTA technique is used to study the thermal stability. Complex impedance analysis is used to calculate the bulk resistance of the complexes. The effect of different plasticizer on the structural and physical properties of polymer blend electrolyte is well correlated.