Poly(vinyl chloride) (PVC)—poly(butyl methacrylate) (PBMA) blended polymer electrolytes with lithium perchlorate (LiClO4) as the complexing salts are prepared by solution casting technique. The addition of PBMA into PVC matrix is found to induce considerable changes in physical and electrical properties of the polymer electrolytes. Addition of PBMA into PVC matrix is found to increase the conductivity by two orders of magnitude (1.108 × 10−5 S cm−1) when compared with that of the pristine PVC polymer electrolyte (10−7 S cm−1). Structural, thermal, mechanical, morphological, and polymer–salt interactions are ascertained from X-ray diffraction (XRD), thermogravimetry/differential thermal analysis (TG/DTA), mechanical analysis, scanning electron microscope (SEM), and Fourier transform infrared spectroscopy (FTIR) respectively. A thermal stability upto 250 °C is asserted from the TG/DTA analysis. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44939. © 2017 Wiley Periodicals, Inc.