The　development　of　low-cost,　stable,　and　recyclable　multiphase　catalysts　in　advanced　oxidation　process　is　essential　for　efficient　degradation　of　antibiotics.　In　this　study,　a　BC-Co-W-700　catalyst　was　used　to　activate　peroxymonosulfate　(PMS)　for　chlortetracycline　(CTC)　degradation.　The　catalyst　was　prepared　using　reclaimed　biomass　material　as　a　matrix.　The　biochar-based　catalyst　possessed　abundant　active　sites　and　realized　the　in-situ　growth　of　Co　and　CoWO4.　The　BC-Co-W-700/PMS　achieved　100%　degradation　of　CTC　(20　mg/L)　within　18　min.　Quenching　and　electron　paramagnetic　resonance　experiments　were　conducted　to　investigate　the　reactive　oxygen　species　(ROS)　in　the　BC-Co-W-700/PMS　system.　The　identified　ROS　in　this　system　included　1O2,　O2[rad]−,　SO4[rad]−,　and　[rad]OH.　Abundant　ROS　endowed　the　system　with　strong　degradation　performance,　applicability,　and　anti-interference　ability.　The　catalytic　mechanism　of　BC-Co-W-700/PMS　system　was　comprehensively　investigated　using　a　combination　of　electrochemical　experiments　and　theoretical　calculations.　The　in-situ　pyrrolic　N　formed　by　biochar　had　a　strong　adsorption　capacity　for　CTC,　allowing　pollutants　to　quickly　adsorb　to　the　catalyst　surface.　This　greatly　shortened　the　distance　required　for　the　catalytic　reaction.　The　introduction　of　W　led　to　abundant　oxygen　vacancies　on　BC-Co-W-700,　causing　the　catalyst　to　produce　a　large　amount　of　1O2.　Furthermore,　the　oxygen　vacancies　provided　a　high　concentration　of　electrons　for　the　conversion　of　Co3+/Co2+.　In　addition,　CTC　degradation　pathways　were　analyzed　using　density　functional　theory　calculations,　and　the　toxicity　of　the　intermediates　was　evaluated　using　the　quantitative　structure–activity　relationship　combined　with　experiments.　The　green　catalyst　synthesis　method　proposed　in　this　paper　could　provide　a　new　approach　for　the　efficient　degradation　of　antibiotics　in　wastewater.　©　2023　Elsevier　B.V.