Poly(acrylonitrile) solutions in dimethylformamide were electrospun to be webs consisting of 300 nm ultrafine fibers. The webs were oxidatively stabilized and activated by steam resulting in activated carbon nanofibers (ACNFs). The specific surface area of the ACNF activated at 700 °C was the highest but mesopore volume fraction of that was lowest. On the other hand, the ACNFs activated at 800 °C showed opposite trends to those activated at 700 °C. The high specific surface area, mainly due to the micropores, introduced maximum specific capacitance at low current density (173 F/g at 10 mA/g). The elevated volume fraction of mesopores gave maximum specific capacitance at high current density (120 F/g at 1000 mA/g). The behavior is explained on the basis of ion mobility in the pores.