Herein,　an　electron-optimized　core-shell　CoFe　alloy-carbon　composite　(CoFeC)　was　developed　from　prepared　CoFe　Prussian　blue　analogues　(CoFe　PBAs)　through　pyrolysis　and　applied　for　peracetic　acid　(PAA)　activation.　Characterization　analysis　and　theoretical　calculations　indicated　that　the　Co　sites　as　the　primary　active　centers,　with　the　presence　of　C　and　Fe　in　CoFeC　significantly　narrowed　the　difference　between　the　d-band　center　(epsilon　d)　and　the　Fermi　level　(EF),　thereby　reducing　PAA　adsorption　energy　on　Co　sites　and　enhancing　electron　transfer.　The　identification　of　reactive　species　confirmed　that　acetylperoxy　radicals　(CH3C(O)OO.)　and　singlet　oxygen　(1O2)　were　the　dominant　species　driving　the　reaction.　The　CoFeC/PAA　system　demonstrated　exceptional　pollutant　degradation　efficiency,　achieving　nearly　100　%　removal　within　30　min,　along　with　strong　interference　resistance　and　high　durability　in　continuous-flow　reactors.　This　work　provided　novel　insights　into　the　activation　of　PAA　by　bimetallic　carbon　catalysts　and　offered　guidance　for　the　development　of　efficient　and　sustainable　water　treatment　technologies.