This work uses a one-step KOH activation for lignin precursors to produce ultra-high mesoporous activated carbons (ACs) with an unprecedented combination of the surface area of 3207 m2 g−1 and mesopore ratio of 76%. The ACs are applied for supercapacitors (SCs) and methylene blue (MB) adsorption. The capacitance of the SCs in the three-electrode system reaches 812.3 F g−1 and demonstrates a remarkable maximum MB adsorption capacity of 1250 mg g−1. By modifying the process conditions, the mesopore ratio of ACs could be controlled from 10% to 80%. Compared with one-step activation, a two-step method produced microporous carbons with a lower surface area of 1227 m2 g−1 and a high micropore ratio of 73%. The capacitance of SCs with two-step ACs reached 228.1 F g−1 and the maximum adsorption capacity of 476.19 mg g−1 for MB adsorption. The two-step method limited the surface area but had a higher oxygen surface functionality, benefiting its electrochemical performance. A techno-economic analysis reveals that the one-step KOH activation-based process develops ACs with a minimum selling price of $7648/ton. This work demonstrates tuning the processing-structure-property-performance relationship of lignin-based ACs to make an economically viable domestic carbon source.