Mesoporous carbon nanofibers as electrode material for electrical double-layer capacitors(EDLCs) are fabricated using the electrospinning method and carbonization. Their morphologies, structures, chemical bonding states, porous structure, and electrochemical performance are investigated. The optimized mesoporous carbon nanofiber has a high sepecific surface area of 667 m2 g−1, high average pore size of 6.3 nm, and high mesopore volume fraction of 80 %, as well as a unifom network structure consiting of a 1-D nanofiber stucture. The optimized mesoporous carbon nanofiber shows outstanding electrochemical performance with high specific capacitance of 87 F g−1 at a current density of 0.1 A g−1, high-rate performance (72 F g−1 at a current density of 20.0 A g−1), and good cycling stability (92 F g−1 after 100 cycles). The improvement of the electrochemical performance via the combined effects of high specific surface area are due to the high mesopore volume fraction of the carbon nanofibers.