The　inefficient　electron　transfer　and　Fe(III)/Fe(II)　cycle　remain　significant　obstacles　in　the　electro-fenton　process.　Herein,　a　nitrogen-doped　graphite　felt　(NGF)-supported　CoFe/CoFe2O4　heterostructure　is　synthesized　that　achieves　highly　efficient　interfacial　electron　transfer　and　stable　Co/Fe　redox　cycle.　Theoretical　calculations　demonstrate　that　the　CoFe/CoFe2O4　heterointerfaces　induce　local　charge　redistribution　benefiting　from　the　electronic　communication　between　electron　acceptor　(CoFe2O4)　and　electron　donor　(CoFe).　Analysis　of　the　Fermi　level　indicates　that　the　introduction　of　CoFe　alloy　enhances　the　electron　density　of　the　catalyst.　The　CoFe/CoFe2O4@NGF　cathode　can　remove　bisphenol　A　(BPA)　completely　in　90　min,　and　the　pseudo-first-order　kinetic　constant　(0.0625　min−1)　is　23　times　higher　than　the　GF　system.　Notably,　the　CoFe/CoFe2O4@NGF　electrode　maintains　excellent　catalytic　capability　and　stability　within　a　broad　pH　range　(3–11).　The　construction　of　the　CoFe/CoFe2O4　heterostructure　reduces　the　adsorption　energy　of　oxygen,　which　ultimately　increases　the　yield　of　reactive　oxygen　species　(ROS).　Quenching　experiments　revealed　that　hydroxyl　radical　(·OH)　played　a　dominant　role　in　the　degradation　of　BPA,　and　significantly　reduced　the　biotoxicity　of　intermediate　products.　This　work　offers　a　dependable　approach　for　developing　bimetallic　catalysts　with　high　catalytic　activity.　©　2024　Elsevier　B.V.