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Biochar derived from waste biomass has proven to be an encouraging novel electrode material in supercapacitors. In this work, luffa sponge-derived activated carbon with a special structure is produced through carbonization and KOH activation. The reduced graphene oxide (rGO) and manganese dioxide (MnO₂) are in-situ synthesized on luffa-activated carbon (LAC) to improve the supercapacitive behavior. The structure and morphology of LAC, LAC-rGO and LAC-rGO-MnO₂ are characterized by the employment of X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), BET analysis, Raman spectroscopy and scanning electron microscopy (SEM). The electrochemical performance of electrodes is performed in two and three-electrode systems. In the asymmetrical two-electrode system, the LAC-rGO-MnO₂//Co₃O₄-rGO device shows high specific capacitance (SC), high-rate capability and excellent cycle reversibly in a wide potential window of 0–1.8 V. The maximum specific capacitance (SC) of the asymmetric device is 586 F g⁻¹ at a scan rate of 2 mV s⁻¹. More importantly, the LAC-rGO-MnO₂//Co₃O₄-rGO device exhibits a specific energy of 31.4 W h kg⁻¹ at a specific power of 400 W kg⁻¹. Overall, the synergistic effect between the ternary structures of microporous LAC, rGO sheets and MnO₂ nanoparticles leads to the introduction of high-performance hierarchical supercapacitor electrodes.