nanofibers stand out as a promising candidate for energy storage applications, particularly in the domain of supercapacitors. Their inherent advantages, including a high surface area, enhanced charge transport capabilities, and improved electrochemical performance, make them an intriguing focus of investigation. In this study, we present a thorough exploration of the synthesis, characterization, and application of PbS nanoparticles incorporated within the electrospun matrix of a polyacrylonitrile−polyaniline (PAN−PANI) blend. The subsequent carbonization process at 700 °C yields carbon nanofibers (CNFs) with tailored structural and electrochemical attributes. The resulting carbonized PbS/PAN−PANI nanofibers (NFs) exhibit exceptional electrochemical properties, including high specific capacitance, specific energy, and specific power, making them promising candidates for supercapacitor applications. Notably, the application of these CNFs in a two-electrode symmetrical supercapacitor device yielded a specific capacitance of 145.6 F g −1 , as determined from galvanostatic charge−discharge (GCD) measurements at a current density of 0.5 A g −1 in a 6 M KOH electrolyte. Furthermore, this device demonstrated remarkable capacitive retention, maintaining 92.45% of its initial capacitance after 10 000 charge−discharge cycles at 1 A g −1 . These outcomes not only affirm the robustness of the fabrication and optimization methodologies but also accentuate the potential of PbS/PAN−PANI CNFs as electrodes for high-performance supercapacitor systems, particularly highlighting their outstanding pseudocapacitive behavior and stability in alkaline electrolytes.