Microporous carbon nanofibers (CNFs) with a high specific surface area were prepared by sol-gel, electrospun, carbonization and pickling processes. Resol type phenolic resin (PF) acted as carbon source, tetraethyl orthosilicate (TEOS) worked as template and polyvinylpyrrolidone worked as spinning additives. The specific surface area and total pore volume of the CNFs were increased obviously with the increased amount of TEOS. A high specific area of 2164 m(2) g(-1,) high microporosity and relatively narrow pore size distribution were achieved. The electrochemical performance was evaluated in 6 M KOH aqueous solution. The microporous CNFs exhibited outstanding electrochemical performance as binder-free electrode of supercapacitors, including a high specific capacitance (316 F g(-2) at 0.2 A g(-1)), considerable rate performance (210 F g(-1) at 20 A g(-1)) and good cycle stability (95% after cycling 1000 times). The microporous CNFs were promising electrode materials for highperformanced supercapacitors. (C) 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.