SO2　removal　is　critical　to　flue　gas　purification.　However,　based　on　performance　and　cost,　materials　under　development　are　hardly　adequate　substitutes　for　active　carbon-based　materials.　Here,　we　engineered　biomass-derived　nanostructured　carbon　nanofibers　integrated　with　highly　dispersed　bimetallic　Ti/CoOx　nanoparticles　through　the　thermal　transition　of　metal-phenolic　functionalized　industrial　leather　wastes　for　synergistic　SO2　adsorption　and　in　situ　catalytic　conversion.　The　generation　of　surface-SO32-　and　peroxide　species　(O22-)　by　Ti/CoOx　achieved　catalytic　conversion　of　adsorbed　SO2　into　value-added　liquid　H2SO4,　which　can　be　discharged　from　porous　nanofibers.　This　approach　can　also　avoid　the　accumulation　of　the　adsorbed　SO2,　thereby　achieving　high　desulfurization　activity　and　a　long　operating　life　over　6000　min,　preceding　current　state-of-the-art　active　carbon-based　desulfurization　materials.　Combined　with　the　techno-economic　and　carbon　footprint　analysis　from　36　areas　in　China,　we　demonstrated　an　economically　viable　and　scalable　solution　for　real-world　SO2　removal　on　the　industrial　scale.　©　2023　American　Chemical　Society.