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Supercapacitors (SCs) have fascinating potential for the energy storage systems of the future due to their exceptional power delivery and quick charge and discharge capabilities. However, its energy density continues to be a barrier to its general use. This study investigates the electrochemical properties of electrospun polyacrylonitrile (PAN) nanofiber (NF) composites embedded with cobalt hydroxide (Co(OH)2) nanoparticles (NPs) for SC electrodes. The synthesis of CNFs involves electrospinning PAN solutions loaded with Co(OH)2 precursors, followed by heat treatment to enhance structural integrity and electrochemical performance. The crystallographic and morphological study of the composite fibres was conducted through different characterization methods. The electrochemical performance of Co3O4/PAN CNFs-based composite electrodes is evaluated through CV, GCD, and EIS measurements, revealing their suitability for SC applications. The findings reveal that the synergistic effects of Co3O4 NPs within the PAN NFs contribute to enhanced specific capacitance, cyclic stability, and rate capability, thus offering significant prospects for the development of high-performance SCs. The Co3O4/PAN CNFs//AC device is constructed using PVA/KOH gel electrolyte, which demonstrated an energy density of 11.19 Whkg−1 at a power density of 1000 Wkg−1. The device exhibits 69% capacitance retention over 3000 cycles at 100 mVs−1, indicating strong cycling stability and electrochemical reversibility, which are crucial for practical applications. [ABSTRACT FROM AUTHOR]