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Summary: The development of efficient methods to achieve a porous activated carbon nanostructures electrode for high‐performance electrochemical double‐layer capacitor (EDLC) is urgently needed at present. In this study, biomass‐based porous hollow carbon nanofiber/nanosheet with suitable micro/mesopores was successfully prepared using a low‐cost simple approach through chemical activation at direct pyrolysis. Biomass‐based porous carbon was performed in two different chemical activation of KOH and ZnCl2. The effects of the different KOH/ZnCl2 concentrations at high‐temperature pyrolysis on the morphological structure and porosity were investigated. The synthesized activated carbon possesses micro/mesopores hollow nanofiber/nanosheet, which enhanced specific surface area from 15.163 m2 g−1 to ultrahigh specific surface area of 1041.900 m2 g−1. These behaviors exhibit a high specific capacitance of 213 F g−1 in a two‐electrode system with excellent energy and power density of 29.6 Wh kg−1 and 106.6 W kg−1 at 1 M H2SO4 aqueous electrolyte. These results provided accurate information about a feasible approach to synthesize biomass‐based porous hollow carbon nanofiber/nanosheet to boost high‐performance energy storage devices. [ABSTRACT FROM AUTHOR]