In the present study, lithium doped vanadium pentoxide Li_xV₂O₅ (0.2 ≤ x ≤ 0.8) specimens have been prepared by the solid-state synthesis method, which possesses an ionic and electronic conducting nature. Lithium incorporates vanadium pentoxide to increase electrical conductivity as well as to enhance energy storage capacity. The undoped V₂O₅ samples show orthorhombic structures, which are slightly tilted towards monoclinic due to lithium doping. These structural and compositional studies have been carried out using X-ray diffraction spectra and X-ray photoelectron spectroscopy. The stretching and vibrational modes of prepared samples are obtained by Fourier Transform Infrared Spectrometer. The significant shifting of optical absorption is observed and hence the optical energy band decreases from 3.37 to 2.44 eV for the present specimens. Electrochemical analysis in the potential window of −0.5 to 0.5 V (scan rate of 5 mV/s) with 2 M KCl electrolyte solution is conducted to get maximum specific capacitance of 529 Fg⁻¹ for Li_0.2V_1.8O_4.6 specimen. The first and fifth cycles of Cyclic Voltammetry suggest that the charging and discharging of Li_xV₂O₅ are in accordance with doped component proportion. The dielectric parameters have been recorded with a frequency response of 10 Hz to 1 MHz. The ac conductivity data has been interpreted by Jonscher’s power law.