Plasticized polymer electrolytes comprising of ethylene carbonate as the plasticizing agent in poly (vinyl chloride) [PVC]–poly (butyl methacrylate) [PBMA] blended polymer electrolytes were prepared by solution casting technique. Complex formation, structural elucidation, conductivity, dielectric parameters (Ɛ′, Ɛ″, M′, and M″), thermal stability, and surface morphology are brought out from FTIR, XRD, ac impedance analysis, dielectric studies, thermogravimetry/differential thermal analysis, and scanning electron microscopic studies, respectively. Polymer electrolytes are found to exhibit higher ionic conductivity at higher concentration of plasticizer at the cost of their mechanical stability. Conductivity of 1.879 × 10−4 S cm−1 is exhibited by the polymer electrolyte consisting of 69% of plasticizer with appreciable thermal stability up to 523 K. Temperature and frequency dependence of conductivity is found to follow Vogel Tammann Fulcher relation and Jonscher power law, respectively. Real and imaginary parts of dielectric constants are found to decrease with increase in frequency which could be due to the electrode polarization effect. © 2017, Springer-Verlag Berlin Heidelberg.