Carbon nanofibers (CNFs) draw great interest due to their noticeable mechanical, electrochemical, and physical properties. In this study, polyacrylonitrile-based CNFs are obtained via electrospinning technique. Thermal oxidation and low temperature (950 degrees C) carbonization are applied to the electrospun web in order to achieve CNF. Through the process, Fourier transform infrared-attenuated total reflectance spectroscopy and Raman spectroscopic results are investigated. The electrochemical properties of the self-standing CNF webs are examined with electrochemical impedance spectroscopy and cyclic voltammetry. In addition, various electrolyte solutions are studied to investigate the capacitive behavior of CNF webs. Electrolyte type variation has a significant effect on the capacitance results and high capacitance values are achieved in aqueous solution. According to the differing electrolyte types, specific capacitance values (C-sp) are recorded between 204 and 149 Fg(-1) where maximum specific capacitance is obtained in 0.5 M H2SO4 as 204 Fg(-1). (c) 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45723.