Peracetic　acid　(PAA),　as　a　disinfectant　with　powerful　oxidation　and　exceptional　antimicrobial　efficiency,　has　gained　considerable　attention　for　its　application　in　advanced　oxidation　processes　(AOPs).　However,　leaching　of　metal　ions　and　low　recovery　efficiency　limited　the　application　of　heterogeneous　AOPs.　Herein,　we　synthesized　a　Co–Fe　bimetallic　oxide　(Co-Fe-O)　derived　from　Prussian　blue　analogs　to　serve　as　an　activator　for　PAA,　efficiently　eliminating　sulfamethazine　(SMZ)　in　a　wide　pH　range　(5–9).　Electron　paramagnetic　resonance　and　quenching　test　revealed　the　coexistence　of　radical　species　in　the　system,　and　R-O·　were　the　main　factors　of　SMZ　elimination.　The　steady-state　model　evaluation　showed　that　3.1　×　10−14　M　R-O·　and　2.05　×　10−14　M　·OH　existed　in　the　system.　Co–Fe　bimetallic　synergies　expedite　the　generation　of　radical　species.　Based　on　density　functional　theory,　the　aniline　ring　and　heterocyclic　ring　of　SMZ　were　regarded　as　the　susceptible　sites　for　radical　attack　and　electron　transfer.　Furthermore,　the　elimination　pathway　of　SMZ　was　proposed　by　combining　the　results　of　intermediate　products.　Additionally,　the　toxicity　of　SMZ　and　intermediates　as　well　as　the　reaction　conditions,　water　matrices,　stability,　and　oxidation　capacity　of　Co-Fe-O/PAA　were　subjected　to　evaluation.　Results　indicate　that　the　Co-Fe-O/PAA　system　has　significant　application　potential　in　the　elimination　of　micropollutants.　©　2024　Elsevier　Ltd