Template-assisted facile synthesis of tubular Co₃O₄ microstructures and its electrochemical performance was studied to understand its use as a potential electrode material for supercapacitors. Tubular porous Co₃O₄ microstructures were synthesized using cotton fibers as bio-template. The as-obtained templated Co₃O₄ structure inherits the morphology and microstructure of cotton fiber. The electrochemical performance of the electrode made up of tubular Co₃O₄ structure was evaluated in 3 M KOH, NaOH, and LiOH aqueous electrolytes. The large-surface-area of tubular Co₃O₄ microstructure has a noticeable pseudocapacitive performance with a capacitance of 401 F/g at 1 A/g and 828 F/g at 2 mV/s, a Coulombic efficiency averaging ~100%, and excellent cycling stability with capacitance retention of about 80% after 5,000 cycles. Overall, the tubular Co₃O₄ microstructure displayed superior electrochemical performance in 3 M KOH electrolyte with peak power density reaching 5,500 W/kg and energy density exceeding 22 Wh/kg. The superior performance of tubular Co₃O₄ microstructure electrode is attributed to its high surface area and adequate pore volume distribution, which allows effective redox reaction and diffusion of hydrated ions. The facile synthesis method can be adapted for preparing various metal oxide microstructures for possible applications in catalysis, electrochemical, sensors, and fuel cells applications.