A carbon nanofiber was produced from the Areca catechu husk as a supercapacitor electrode, utilizing a chemical activation of potassium hydroxide (KOH) at different concentrations. One-stage integrated pyrolysis both carbonization and physical activation were employed for directly converting biomass to activated carbon nanofiber. The morphology structure, specific surface area, pore structure characteristic, crystallinity, and surface compound were characterized to evaluate the influence on electrochemical performance. The electrochemical performance of the supercapacitor was measured using cyclic voltammetry (CV) through a symmetrical system in 1 M H2SO4. The results show that the KOH-assisted or absence activation converts activated carbon from aggregate into a unique structure of nanofiber. The optimized carbon nanofiber showed the large specific surface area of 838.64 m2 g−1 with the total pore volume of 0.448 cm3 g−1, for enhancing electrochemical performance. Beneficial form its unique structural advantages, the optimized carbon nanofiber exhibits high electrochemical performance, including a specific capacitance of 181.96 F g−1 and maximum energy density of 25.27 Wh kg−1 for the power density of 91.07 W kg−1. This study examines a facile conventional route for producing carbon nanofiber from biomass Areca catechu husk in economical and efficient for electrode supercapacitor.