The　homogeneous　electro-Fenton(EF)　technique　is　widely　recognized　in　water　treatment　for　its　efficient　generation　of　hydroxyl　radicals　(center　dot　OH).　However,　its　drawbacks,　such　as　iron　sludge　formation　and　strict　pH　requirements,　constrain　its　practical　applications.　To　overcome　these　limitations,　this　study　developed　an　ironmodified　self-breathing　electrode　(Fe3O4/MGFif)　through　impregnation　and　filtration,　characterized　it,　and　applied　it　to　construct　a　heterogeneous　EF　system　for　treating　nanofiltration　concentrates　(NFCs).　Under　optimal　conditions,　the　Fe3O4/MGFif　electrode　achieved　COD　and　TOC　removal　efficiencies　of　74.2　+/-　1.8　%　and　81.6　+/-　1.7　%,　respectively,　within　2　h.　Moreover,　the　modified　electrode　demonstrated　degradation　efficiency　in　the　heterogeneous　EF　system　comparable　to　that　in　the　homogeneous　EF　system,　while　eliminating　iron　sludge　formation　and　expanding　the　applicable　pH　range.　Radical　scavenging,　quenching　experiments　and　electron　paramagnetic　resonance　(EPR)　technique　demonstrated　that　the　electrode　generated　substantial　center　dot　OH　and　minor　amounts　of　superoxide　radicals　(center　dot　O2-)　during　NFCs　degradation.　The　ultraviolet　fluorescence　spectra　and　threedimensional　fluorescence　spectra　indicated　that　reactive　radicals　efficiently　degraded　humic　substances　in　NFCs,　reduced　aromatization,　and　significantly　enhanced　biochemical　properties.　This　study　resolves　the　challenges　of　iron　sludge　formation　and　pH　constraints　in　homogeneous　EF-based　NFCs　treatment　and　proposes　a　novel　pathway　capable　of　efficiently　degrading　recalcitrant　organic　pollutants　by　self-breathing.