Nanostructured material like FeSe2 has been synthesized through a simple and cost-effective hydrothermal method. The effect of cationic, non-ionic, and anionic surfactants has been studied on the structural, morphological, and electrochemical properties of FeSe2 electrode material. The FeSe2 electrode material prepared with the assistance of CTAB surfactant displayed a superior specific capacitance value of 401 F g −1 at a scan rate of 10 mV s −1 and 337 F g −1 at a current density of 3.3 A g −1, respectively. The maximum energy density of the symmetric supercapacitor cell fabricated with the same material is evaluated to be 47 Wh kg−1 at a power density of 1667 W kg−1. The addition of the surfactant cetyltrimethylammonium bromide (CTAB) during the synthesis process is found to have a significant impact on the charge storage capability of the material, which is attributed to an increase in active surface area, porosity, reduced crystallite size, and reduced bulk resistance, etc. The real-time use of CTAB-based FeSe2 symmetric cells has been verified via illuminating different voltage light-emitting diodes. Further, the electronic properties and the quantum capacitance of FeSe2 material synthesized without the assistance of any surfactant have been analyzed theoretically using first-principles density functional theory calculations. Acquired results unveil the potential growth of FeSe2 electrode material in energy storage applications.