A hybrid electrode structure consisting of amino functionalised multi-walled carbon nanotube, nickel sulphide, and polypyrrole is successfully synthesized using a two-step synthesis such as hydrothermal and in-situ polymerization method. The resulting MWCNT/NiS/PPy composite exhibits a distinct tube-in-tube morphology with excellent stratification. The combination of different components and the unique structure of the composite contribute to its impressive specific capacitance of 1755 F g−1 at 3 A g−1. The prepared ternary composite enables ample exposure of numerous active sites while improving structural stability, ultimately leading to enhanced energy storage capabilities. They do this by combining the advantages of constituent components, a hierarchical assembly approach, and an integrated composite structure. Furthermore, even after undergoing 10,000 charge-discharge cycles, the supercapacitor retains more than 97% of columbic efficiency. An asymmetric coin cell was fabricated using MWCNT/NiS/PPy//AC device which delivered an energy density and power density of 33.12 Wh Kg−1 and 6750 W kg−1 respectively. These findings highlight the exceptional potential of the fabricated device for future applications in hybrid energy storage systems.