Our research has led to a significant breakthrough in the field of energy storage. For the first time, we have prepared a series of highly porous sulfur-doped activated carbon derived from natural biomass sugarcane bagasse. The sulfur-doped waste sugarcane bagasse-derived activated carbon (WSC/S) possess a unique properties of large specific surface area (SSA) with high mesoporosity, better wettability, and numerous redox active dopant sites. These unique properties of WSC/S significantly enhance supercapacitor functionality. There are a large number of mesopores on the WSC/S, which shorten the ion diffusion path length and make their ion transport efficient. As the results of that the WSC/S achieved a high specific capacitance of 282.25 Fg−1 with a current density of 0.1 Ag−1 and excellent cycling stability with >96 % capacitance retention after 10,000 cycles in 6 M KOH electrolyte. We explored WSC/S as an anode material to fabricate an asymmetric supercapacitor (ASC) device, where activated carbon cloth was used as a cathode. The ASC device showed an energy density of 43.26 Wh kg−1 with a power density of 0.1 kW kg−1 at a current density of 0.1 Ag−1, which is superior to that obtained for symmetric WSC/S//WSC/S supercapacitor. These performances indicate the potential of the WSC/S for high-performance energy storage systems.