This work essentially offers a new kind of V2O5/Na0.33V2O5 as electrochemical active material for the development of Li+ ion redox supercapacitors. Here, polycrystalline mixed phase of V2O5/Na0.33V2O5 (V/Na) nanostructures are synthesized via simple co-precipitation technique. The various molar ratio of precipitator (NaOH) in the synthesis process displays different nanostructures of V/Na. The structural and morphological properties of V/Na samples are studied using physico-chemical analysis methods. The electrochemical properties of V/Na nanostructured samples are performed using cyclic voltammetry, galvanostatic charge/discharge test and electrochemical impedance spectroscopy techniques in 1M LiClO4 aqueous electrolyte. The sample V/Na synthesized using equimolar ratio of vanadium salt and precipitator displayed nanopellet morphology, which exhibited the highest capacitance value of 334Fg−1 at 1 Ag−1 discharge current density. Moreover, these polycrystalline V/Na nanostructured electrodes show excellent electrochemical properties with comparable stability after 1000 charge/discharge cycles.