<p>Ionic liquid based electrolytes for energy storage devices pose vulnerabilities such as internal short circuits and thermal runaway. To mitigate these issues, solid/quasi solid polymer electrolytes have been introduced due to their enhanced safety and flexibility. Alkali metal salts provide effective charge carriers that facilitate ion transport when combined with poly (vinyl alcohol) (PVA), which renders a conduction pathway to a greater extent and stays superiorly flexible and mechanically stable without significantly compromising conductivity. In this work, a high lithium-ion conducting polymer electrolyte based on PVA/LiClO₄ was investigated and prepared by a solution-casting method. The structural characteristics and interactions between LiClO₄ and PVA within the electrolyte matrix were studied using X-ray diffraction (XRD) and Fourier-transform infrared (FTIR) spectroscopy analyses, respectively. The resistivity, dielectric and other electrical properties were explored through electrochemical impedance spectroscopy (EIS). Among the various compositions investigated, the sample with a LiClO₄:PVA ratio of 1.5:1 exhibited a maximum ionic conductivity of 8.2⋅10^− 4 S/cm at room temperature, accompanied by dominant ionic mobility and enhanced dielectric polarization. Furthermore, the EIS analysis revealed the factors affecting the conductivity and shows the conduction type mechanism and relaxation behaviour of the polymer electrolyte at a certain frequency. The enhanced ionic conductivity may be due to the combined effects of several mechanisms (Solid electrolyte interface (SEI) formation, dielectric and thermionic polarization, conductive and viscoelastic relaxation, and ion-hopping transport). These characteristics make the developed polymer electrolyte a promising candidate for flexible energy storage applications.</p>