Microporous carbon nanofibers (Mi-CNFs) and mesoporous carbon nanofibers (Me-CNFs) with high surface area were prepared by electrospinning resol resin/PVP/TEOS/F127 ethanol solution, followed by curing, carbonization and pickling process. TEOS was responsible for structural stability and producing micropores, while F127 for forming mesopores. Mi-CNFs showed high specific surface area of 1841 m2 g-1, while Me-CNFs possessed both high specific surface area of 1674 m2 g-1 and mesoporosity of 64%. The electrochemical test revealed that Mi-CNFs had higher capacitance (276 F g-1 at 0.5 A g-1) and Me-CNFs possessed higher capacitance retention (71%, 150 F g-1 at 30 A g-1).