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Concerns associated with global warming and the depleting reserves of fossil fuels have highlighted the importance of high−performance energy storage systems (ESSs) for efficient energy usage. ESSs such as supercapacitors can contribute to improved power quality of an energy generation system, which is characterized by a slow load response. Composite materials are primarily used as supercapacitor electrodes because they can compensate for the disadvantages of carbon or metal oxide electrode materials. In this study, a composite of oxide nanoparticles loaded on a carbon nanofiber support was used as an electrode material for a hybrid supercapacitor. The addition of a small amount of hydrophilic FeN@GnP (Fe− and N−doped graphene nanoplates) modified the surface properties of carbon nanofibers prepared by electrospinning. Accordingly, the effects of the hydrophobic/hydrophilic surface properties of the nanofiber support on the morphology of Co3O4 nanoparticles loaded on the nanofiber, as well as the performance of the supercapacitor, were systematically investigated.