This study presents the successful synthesis and characterization of polyaniline (PANI), PANI/reduced graphene oxide PANI/rGO (PR), and PANI/rGO/ZnO (PRZ) nanocomposites as electrode materials for supercapacitors. Employing electrospinning and electrospraying techniques, we developed nanofibrous composites with enhanced structural and electrochemical properties. The addition of rGO and ZnO in the PRZ composite significantly improved specific capacitance, stability, and charge‐transfer efficiency. Electrochemical analyses, including cyclic voltammetry (CV), galvanostatic charge–discharge (GCD), and electrochemical impedance spectroscopy (EIS), revealed a peak specific capacitance of 845 F g−1 at 0.5 A g−1 for PRZ, outperforming PR (395 F g−1), and PANI (140 F g−1). These enhancements are attributed to the synergistic effects of carbon‐based and pseudocapacitive components, resulting in higher conductivity, improved redox activity, and reduced internal resistance. Additionally, the PRZ composite exhibited excellent cyclic stability, retaining 89% of its capacitance over 5000 cycles, underscoring its durability and suitability for long‐term energy storage applications.