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 m(2) g(-1), while Me-CNFs possessed both high specific surface area of 1674 m(2) 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)).