<p>The development of high-performance, cost-effective electrode materials are critical for meeting the growing demand for efficient energy-storage systems. In this work, a NiCo₂O₄/MWCNT composite was synthesized through a simple and scalable dry-grinding approach followed by low-temperature annealing, yielding core/shell-like hybrid architecture. Structural analyses (XRD, Raman, FTIR, FESEM, TEM, and SAED) confirmed the formation of phase-pure cubic spinel NiCo₂O₄ uniformly anchored onto multi-walled carbon nanotubes, while XPS characterization revealed the coexistence of Ni²⁺/Ni³⁺ and Co²⁺/Co³⁺ centers and an increased concentration of oxygen vacancies in the composite. These features, combined with the conductive MWCNT network, enhance electron mobility, provide abundant electroactive sites, and facilitate rapid ion diffusion. Electrochemical evaluation demonstrated outstanding supercapacitive performance, with the composite delivering a high specific capacitance of 1400 F g⁻¹ at 1 A g⁻¹, excellent rate capability, and superior long-term cycling stability, retaining 94% capacitance after 5000 cycles with nearly 100% coulombic efficiency. The device delivered an energy density of 25.8 Wh kg⁻¹ at a power density of 892 W kg⁻¹ and retained 20.4 Wh kg⁻¹ even at an ultrahigh power density of 26880 W kg⁻¹, confirming its suitability for practical energy-storage applications. Dunn’s method revealed a balanced hybrid charge-storage mechanism, with capacitive contributions increasing from 46 to 52% across increasing scan rates, consistent with fast redox kinetics and low charge-transfer resistance observed in EIS analysis. Overall, the synergistic interaction between NiCo₂O₄ nanoparticles and MWCNTs significantly boosts electrochemical performance, establishing the NiCo₂O₄/MWCNT hybrid as a promising electrode material for next-generation high-power supercapacitors.</p>