AbstractA facile ternary nanocomposite comprising of polyaniline, titanium dioxide, polypyrrole, that is, PANI‐TiO2‐PPy was synthesized by in‐situ chemical oxidative polymerization method and fabricated as an active electrode material for supercapacitor applications. The phase, morphology, chemical composition, electronic states and thermal behavior of PANI‐TiO2‐PPy were analyzed using XRD, FESEM/EDAX, FTIR, XPS, and TGA techniques. CV profile of PANI‐TiO2‐PPy electrode exhibits the highest specific capacitance (600 F g−1) at 1 mV/s in 1 M KOH electrolyte, which is higher than the PANI (31 F g−1), PPy (120 F g−1), and TiO2 (398 F g−1) electrodes. The charge storage mechanism of PANI‐TiO2‐PPy electrode was also explored in 1 M H2SO4 and 1 M Na2SO4 electrolytes; wherein the capacitive behavior of ternary electrode was found to be superior in alkaline electrolyte compared to acidic and neutral electrolytes. From GCD, the ternary electrode exhibited the longest charge/discharge curve when compared to unary electrodes, which affirms the improved energy storage capacity of PANI‐TiO2‐PPy. The lower ESR value (0.90 Ω) exhibited by ternary electrode in comparison with PANI (1.75 Ω), PPy (1.59 Ω), and TiO2 (2.11 Ω) and 92% of capacitive retention after 2500 charge/discharge cycles suggest that PANI‐TiO2‐PPy could be a suitable active electrode for supercapacitors.