A novel Lithium triflate-incorporated Solid Polymer Electrolyte (SPE) has been developed by using the optimized blend of Ghatti Gum (GG) and Xanthan Gum (XG) with a biodegradable synthetic polymer, Polyvinyl alcohol (PVA), ethylene glycol as a plasticizer, and formaldehyde as a cross-linker for energy storage applications. They are examined by X-ray diffraction, Fourier transform infrared spectroscopy, and electrochemical impedance analysis. The frequency-dependent conductivity adheres to Joshner’s universal power law, with the TF10 composition achieving the higher ionic conductivity of 2.73 × 10⁻⁵ S cm⁻¹. Temperature-dependent conductivity confirms Arrhenius-type behavior and shows a low activation energy of 0.15 eV that supports facile ion transport. The conduction process in TF10 follows the Correlated Barrier Hopping (CBH) model. Dielectric and modulus investigations indicate relaxation dynamics with the shorter relaxation time (6.45 × 10⁻⁶ s) from tangent loss spectra. From the SEM analysis, the uniform distribution and the porous nature of the electrode activated carbon are confirmed. A supercapacitor is assembled with TF10 displays electric double-layer capacitive features, delivering a specific capacitance of 7.1 Fg⁻¹ at 15 mVs⁻¹. Charge–discharge analysis reveals energy and power densities of 2.52 Wh kg⁻¹ and 2500 W kg⁻¹, respectively, for the supercapacitor.