The O-N-S co-doped hierarchical porous carbons are prepared by direct pyrolysis of kraft lignin which is the byproduct from papermaking black liquor. The proposed preparation method is extremely facile, green-environmental, and low-cost without any additional activating agents, additives or templates. The kraft lignin-derived carbon materials possess large specific surface areas (338−1307 m2 g−1), hierarchical porous structures and abundant multi-heteroatoms co-doping (9.84–19.91 wt%). Benefiting from above synergistic advantages, the as-fabricated symmetric supercapacitor in aqueous electrolyte delivers a high specific capacitance of 244.5 F g−1 at 0.2 A g−1, excellent rate-capability (81.8% retention of initial capacitance at 40.0 A g−1), and outstanding cycling stability (91.6% retention over 10000 cycles). Importantly, this device in aqueous electrolyte delivers an energy density of 8.5 W h kg−1 at a power density of 100 W kg−1. Furthermore, a remarkable energy density of 66.8 W h kg−1 at a power density of 1.75 kW kg−1 has been achieved and 32.2 W h kg−1 is still maintained even at an ultrahigh power density of 40.0 kW kg−1 when ionic liquid serves as electrolyte. This study demonstrates the successful conversion of low-valued natural biomass derivative into sustainable high-performance supercapacitor electrode materials with a simple, low-cost, and green-environmental production process.