In this study, we investigate the electrochemical properties of a nickel oxide-carbon (NiO/C) material, synthesized in the form of highly porous carbon nanofibers through the electrospinning of polymers such as polyacrylonitrile (PAN) and polystyrene (PS) followed by a carbonization process. The primary focus of this work is to determine the optimal mixing ratio for the hybrid material composed of NiO and carbon. While it is widely acknowledged that supercapacitor materials benefit from having a high specific surface area, our findings reveal that hybrid carbon nanofibers with a 45% specific carbon-to-nickel oxide ratio exhibit significantly enhanced capacitance (39.9 F g−1). This outcome suggests the promising potential of our materials as an energy storage material for hybrid supercapacitors, combining the advantages of electric double-layer capacitors (EDLC) and Pseudo capacitors (Pseudo).