The purpose of this work was to investigate the performance of electrodes synthesized with Polyacrylonitrile-based carbon nanofibers (PAN-based CNFs). The homogenous PAN solutions with different concentrations were prepared and electrospun to acquire PAN nanofibers and then CNFs were fabricated by heat treatment. The effective parameters for the production of electrospun CNF electrode were investigated. Scanning electron microscopy (SEM) was used to characterize electrospun nanofibers. Cyclic voltammetry was applied to investigate the changes of behavior of electrospun CNF electrodes with different diameters. The structure of CNFs was also evaluated via X-ray diffraction (XRD) and Raman spectroscopy. The results exhibited that diameter of nanofibers reduced with decreasing polymer concentration and applied voltage and increasing tip-to-collector distance, while feeding rate did not have significant effect on nanofiber diameter. The investigations of electrochemical behavior also demonstrated that cyclic voltammetric response improved as diameter of CNFs electrode decreased.