Reclaiming biomass waste to carbon cathode is promising to construct a sustainable electrochemical system. Here, we developed a novel thermal foaming process to reform kraft lignin to a free-standing and multi-porous carbon foam, which can be used as carbon cathode for electro-Fenton treatment of emerging contaminants (ECs). Benefiting from the excellent physicochemical and electrochemical properties with multi-porous and graphitic structure, the synthesized carbon foam cathode enhanced the electrocatalytic generation of H2O2 and ?OH, and subsequently promoted the mass transfer and interactions among reactants (i.e., O2, H2O2, Fe2+, ?OH, natural organic matters, and ECs). Eventually, an efficient degradation of ECs was achieved most likely via the multi-step ?OH addition, cleavage, and ring opening reactions. Overall, the outcomes of this work provide a sustainable and applicable design and strategy to upgrade lignin-containing biomass to carbon cathode for efficient ECs remediation.