In this article, a facile two-step activation method, coupled with phosphoric acid (H₃PO₄)-assisted pretreatment and followed KOH activation, was reported for constructing hierarchical porous carbon (HPC) materials derived from lignin. The introduction of H₃PO₄, cross-linked with lignin sources generated phosphate (and/or polyphosphate) ester groups throughout the lignin structure, which endowed the pre-activated intermediate char (IC) with a hierarchical porous structure. Such phosphate esters contributed to the multi-scale pore structure within the pre-activated IC, which was beneficial for the uniform distribution and impregnation of subsequent KOH activators, thus leading to the formation of HPC materials. The as-prepared HPC exhibited a large specific surface area (SSA) of 1345.1 m²/g, which ensures the accessibility of the ion diffusion pathways. The supercapacitors integrated with HPC delivered a high specific capacitance of 241 F/g (in a three-electrode system) and outstanding rate capability with an 80.9% capacitance retention from 0.5 A/g to an ultra-high current density of 50 A/g.