A high‐performance symmetric supercapacitor was fabricated using a Na_0.33V₂O₅ nanocomposite synthesized by means of a simple co‐precipitation technique. The structural and morphological investigation showed that the synthesized Na_0.33V₂O₅ nanocomposite exhibited a monoclinic structure with a nanorod‐like morphology. The electrochemical properties of the Na_0.33V₂O₅ symmetric supercapacitor were studied utilizing three different aqueous electrolytes, such as 1 M of LiCl_, NaCl and KCl, respectively. Interestingly, the fabricated Na_0.33V₂O₅ symmetric supercapacitors exhibited excellent electrochemical capacitance behaviour in all the electrolytes with a maximum specific capacitance value of 168 F g⁻¹ in 1 M LiCl, 146 F g⁻¹ in 1 M NaCl and 132 F g⁻¹ in 1 M KCl electrolytes at 0.5 A g⁻¹ discharge current density. In addition, Na_0.33V₂O₅ symmetric supercapacitors demonstrated an excellent cyclic stability in 1 M NaCl electrolyte with high capacitance retention of approximately 81 % after 50 000 charge/discharge cycles.