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Hierarchical porous carbon-based electrodes, benefiting from their facilitated ion diffusion and electron conduction, have demonstrated enormous potential in supercapacitors. The preparation of hierarchical carbons with uniformity and appropriate porosity, however, still remains a grand challenge, which hinders their widespread applications. Herein, a hierarchical porous polyimide-derived carbon electrode (CPC-Fe/Zn) has been fabricated by employing bimetallic salts (Fe/Zn) as precursor and template to activate the cellulose/polyimide (PI) carbon (CPC). Originating from suitable distribution of mesopores and micropores, the obtained CPC-Fe/Zn delivers a high specific capacitance of 420 F/g at a current density of 1 A/g. Moreover, a symmetric supercapacitor device assembled with CPC-Fe/Zn exhibits delivers an energy density of 35.5 Wh/kg at a power density of 800 W/kg. Even at a larger current density of 20 A/g, the specific capacitance retention of such device still remains 92.5 % after 10,000 cycles, showing the rate performance and stability. This work has proposed a bimetallic salts template-assisted strategy to precisely modulate of the pore structure of carbon electrodes, which provides a promising platform to design superior electrodes for various electrochemical systems. [Display omitted] • The hierarchically porous structure of the material can be modulated precisely. • The symmetric supercapacitor exhibited a remarkable energy density of 35.5 Wh/kg @ 1000 W/kg. • The specific capacitance retention of symmetric supercapacitor reached 92.5 % after 10,000 cycles. [ABSTRACT FROM AUTHOR]