Activated carbon nanofibers(ACNF) were prepared from polyacrylonitrile (PAN)-based nanofibersusing CO2 activation methods with varying activation process times. The surface and structural characteristics of the ACNF were observed by scanning electron microscopy and X-ray diffraction, respectively. N2 adsorption isotherm characteristics at 77 K were con-firmedby Brunauer-Emmett-Teller and Dubinin-Radushkevich equations. As experimental results, many holes or cavernous structures were found on the fibersurfaces after the CO2 activation as confirmedby scanning electron microscopy analysis. Specificsurface areas and pore volumes of the prepared ACNFs were enhanced within a range of 10 to 30 min of acti-vation times. Performance of the porous PAN-based nanofibersas an electrode for electrical double layer capacitors was evaluated in terms of the activation conditions.