BackgroundThe non-metallic carbon catalyst in oxygen reduction reaction (ORR) is mainly hindered by their low catalytic activity and high cost. MethodsNovel hierarchical porous carbons (HPCs) with N, S codoping were synthesized from WPCBs based on the crab shell templates accompanied by different KOH activation temperatures and the modification of IL. Significant findingsOwing to the ordered hierarchical porous structure, HPCs-850 have large SBET (2209 m2/g) and high Vtot (1.389 cm3/g). After IL modification, N and S elements are successfully introduced into the carbon network of HPCs-850 to synthesize LHPCs-850. In an alkaline medium, the reduction potential, initial voltage, half-wave potential, and limiting current density of LHPCs-850 are 0.68 V, 1.05 V, 0.78 V, and 4.9 mA/cm2, demonstrating LHPCs-850 have excellent ORR catalytic performance. After 18,000 s durable measurement, the relative current density of LHPCs-850 still keeps 92% of its initial current density, which is more stable than that of HPCs-850 (87%). DFT calculation confirms that N, S codoping can improve catalytic activity by providing additional ORR active sites number. The proposed route to prepare WPCBs-based LHPCs broadens a new field of large-scale synthesis of electrocatalytic materials from industrial wastes.