Electro-Fenton　(EF)　process　stands　out　as　an　energy-efficient　and　highly　promising　advanced　oxidation　technology　for　organic　contaminants　degradation.　However,　achieving　optimal　heterogeneous　catalytic　conditions　for　simultaneous　H2O2　generation　and　spontaneous　Fe2+　regeneration　poses　difficulties　in　conventional　EF.　This　is　due　to　the　electric　potential　difference　between　H2O2　generation　and　Fe2+　regeneration　at　a　single　cathode.　Therefore,　the　boron　doped　biochar　modified　dual-cathode　EF　(DCEF)　system　was　designed　in　this　work　to　overcome　the　defect　of　conventional　EF　system,　which　not　only　demonstrated　outstanding　accumulation　of　H2O2　(＞300　mg　L-1)　but　also　exhibited　a　remarkable　capability　of　degradation　(＞90　%).　Furthermore,　the　system　could　also　adapt　to　a　broad　pH　range　of　3–11.　The　superior　doxycycline　(DOX)　degradation　efficiency　of　DCEF　system　could　be　attributed　to　the　dominant　role　played　by　C=O　and　BCO2　groups　in　the　activation　of　H2O2　and　subsequently　generating　reactive　oxygen　species　(ROSs),　as　revealed　by　XPS　analysis　and　DFT　calculation.　In　addition,　the　DCEF　system　achieved　an　impressive　TOC　removal　efficiency　of　70.5　%　and　a　minimal　energy　consumption　(EC)　of　0.32　kWh　(g　TOC)-1.　Therefore,　this　work　introduced　a　DCEF　system　to　address　the　challenges　of　conventional　EF　system,　which　shed　light　on　the　design　of　wastewater　treatment　technology　and　lied　the　groundwork　for　a　strategy　of　resource　utilization.　©　2024　Elsevier　B.V.