Electrospun metal oxide-embedded carbon nanofibers have attracted considerable attention in energy storage applications for the development and fabrication of supercapacitors owing to their unique properties such as flexibility, high capacitance, large specific surface areas, and morphological and conductivity properties. Herein, a novel zirconia-based carbon nanofiber (referred to as CNF-20ZrO₂) was fabricated using a simple electrospinning method and applied to a supercapacitor as the electroactive material for the first time. The optimal electrode (CNF-20ZrO₂) demonstrates a high specific capacitance of 140 F/g at 1 A/g. In addition, the assembled supercapacitor delivers maximum specific energy of 4.86 Wh/kg at a specific power of 250 W/kg and shows excellent cycling stability of 82.6% after 10 000 cycles at 1 A/g. The electrochemical performance of the electrode originates from the high content of nitrogen and oxygen species, abundant electrochemical active sites, and high ionic conductivity.