Nanosheet-like structures of copper cobaltite (CuO/Co2O4) decorated on N-MWCNT electrodes were synthesized through hydrothermal process in the presence of ammonia/urea. The structural and morphological properties were characterized by Raman, XRD, XPS, SEM, SEM-EDX and FE-TEM analysis. The electrochemical properties of the CuO/Co2O4@N-MWCNT hybrid electrodes were studied using cyclic voltammetry, galvanostatic charge−discharge, and electrochemical impedance analyses. The prepared CuO/Co2O4@N-MWCNT and CuO@N-MWCNT electrodes showed a specific capacitance of ∼246 F g−1 and 100 F g−1 at a current density of 0.5 A g−1 for three electrode assembly. Further, the asymmetric cells also fabricated and it delivered the highest specific capacitance of 268 F g−1 and 279 F g−1 for CuO@N-MWCNT and CuO/Co2O4@N-MWCNT electrodes respectively. These electrodes possessed very good capacitance behavior with 89% retention even after 5000 cycles at 0.5 A g−1 which overlay a way to use as promising candidates for the high-performance supercapacitors.