To improve the performance of carbon nanofibers as electrode material in electrical double-layer capacitors (EDLCs), we prepare three types of samples with different pore control by electrospinning. The speciments display different surface structures, melting behavior, and electrochemical performance according to the process. Carbon nanofibers with two complex treatment processes show improved performance over the other samples. The mesoporous carbon nanofibers (sample C), which have the optimal conditions, have a high sepecific surface area of 696 m2 g-1, a high average pore diameter of 6.28 nm, and a high mesopore volume ratio of 87.1%. In addition, the electrochemical properties have a high specific capacitance of 110.1 F g-1 at a current density of 0.1 A g-1 and an excellent cycling stability of 84.8% after 3,000 cycles at a current density of 0.1 A g-1. Thus, we explain the improved electrochemical performance by the higher reaction area due to an increased surface area and a faster diffusion path due to the increased volume fraction of the mesopores. Consequently, the mesoporous carbon nanofibers are demonstrated to be a very promising material for use as electrode materials of high-performance EDLCs.