Carbon nanofibers are prepared via the electrospinning method accompanied by the phase-separation process using polyacrylonitrile as a carbon precursor. Effects of preoxidation and carbonation temperatures on electrochemical performance are studied and optimized in detail. The morphology and porous structure are characterized by scanning electron microscope, transmission electron microscope, and nitrogen adsorption and desorption measurements, respectively; the electrochemical performances are measured by the CHI660E workstation. The results show that the diameter of carbon nanofibers is about 150–200 nm with a uniform and smooth surface. The optimized preoxidation temperature is 280 °C with a carbonation temperature of 700 °C. The highest capacitance is up to 155 F/g, and the symmetric supercapacitor delivers a maximum energy density of 7.78 W h/kg with a power density of 400 W/kg and a maximum power density of 4000 W/kg with an energy density of 2.0 W h/kg. The symmetric supercapacitor also exhibits good cycle stability 91.0% of initial specific capacitance after 5000 cycles.