In this project, we present a comparative study of the electrochemical performance for tubular MCo2O4 (M = Cr, Mn, Ni) microstructures prepared using cotton fiber as a bio-template. Crystal structure, surface properties, morphology, and electrochemical properties of MCo2O4 are characterized using X-ray diffraction (XRD), gas adsorption, scanning electron microscopy (SEM), Fourier transforms infrared spectroscopy (FTIR), cyclic voltammetry (CV), and galvanostatic charge-discharge cycling (GCD). The electrochemical performance of the electrode made up of tubular MCo2O4 structures was evaluated in aqueous 3M KOH electrolytes. The as-obtained templated MCo2O4 microstructures inherit the tubular morphology. The large-surface-area of tubular microstructures leads to a noticeable pseudocapacitive property with the excellent electrochemical performance of NiCo2O4 with specific capacitance value exceeding 407.2 F/g at 2 mV/s scan rate. In addition, a Coulombic efficiency ~100%, and excellent cycling stability with 100% capacitance retention for MCo2O4 was noted even after 5000 cycles. These tubular MCo2O4 microstructure display peak power density is exceeding 7000 W/Kg. The superior performance of the tubular MCo2O4 microstructure electrode is attributed to their high surface area, adequate pore volume distribution, and active carbon matrix, which allows effective redox reaction and diffusion of hydrated ions.