The widespread applications of vanadium pentoxide (V2O5) are limited because of its low electrical conductivity and restricted ion diffusion coefficient. To address these constraints, the present study includes a straightforward and effective approach for fabricating polyaniline based silver-decorated vanadium pentoxide (Ag-V2O5/PANi) as an electrode material. The structural and morphological investigation of prepared electrode materials were made by X-ray diffraction analysis and scanning electron microscopy respectively. In comparison to pure Ag-V2O5, the Ag-V2O5/PANi composite demonstrated enhanced performance in various aspects. Specifically, the Ag-V2O5/PANi showed a higher specific capacitance (628 Fg−1) when subjected to a current density (1 Ag−1) in KOH electrolyte. Additionally, it has an energy density of 153 Whkg−1. Furthermore, the Ag-V2O5/PANi composite exhibited superior stability even after undergoing 3000 charge to discharge cycles. Exceptional capabilities shown can be ascribed to synergistic interaction between PANi and Ag-V2O5. The remarkable outcomes obtained from these electrode materials have the potential to foster novel prospects in high-energy-density storage systems.