Hybrid materials are essential materials for the future age elite electrochemical supercapacitors. A hybrid material or organic polymer‐inorganic metal oxide composite comprises of polyaniline (PANI) with fly ash (FA) is made by in‐situ polymerization of aniline monomer with fly ash, an inexhaustible asset. The impact of fly ash on polyaniline is resolved from electrical and electrochemical measurements. PANI‐FA is utilized in a supercapacitor cell as the electrode. FT‐IR, XRD, FE‐SEM, TGA and BET evaluate properties of this hybrid, and their electrochemical properties are assessed by CV, CD, and EIS measurements. PANI with 10 wt.% of FA (PANI‐FA01) indicates higher conductivity and supercapacitor execution than its individual material via metal oxide, acting as an intermediate for transferring ions from PANI and electrolyte. PANI‐FA01 demonstrates a higher capacitance estimation of 208 F g−1 contrasted with PANI (83 F g−1) at 2.5 A g−1. The hybrid electrode material shows better charge‐discharge cycles, holding over 66 % of its first cycle gravimetric capacitance after 5000 cycles with effective coulombic efficiency of 99–100 %, which is as yet 43 % higher than the specific capacity of PANI. The Bode plot shows a phase angle of 80°.