Recently,　a　novel　2-electron　oxygen　reduction　reaction　(ORR)　based　electro-oxidation　(EO)　system　was　developed,　which　utilizes　a　H2　O2　generation　cathode　instead　of　H2　evolution　cathode.　A　Ti-based　Ni-Sb　co-doped　SnO2　(Ti/NATO)　anode　was　selected　for　efficient　degradation　of　refractory　organics　and　O3　production.　The　synergistic　reaction　of　O3　/H2　O2　further　accelerated　the　generation　of　hydroxyl　radicals　(center　dot　OH)　in　the　ORR-EO　system.　However,　the　catalytic　activity　and　long-term　effectiveness　of　the　Ti/NATO　anode　limited　the　large-scale　application　of　the　ORR-EO　process.　In　this　study,　a　blue　TiO2　nanotube　array　(blue-TiO2　-NTA)　inter-layer　was　introduced　into　the　fabrication　process　between　the　Ti　substrate　and　NATO　catalyst　layer.　Compared　to　the　Ti/NATO　anode,　the　Ti/blue-TiO2　-NTA/NATO　anode　achieved　higher　efficiency　of　organic　removal　and　O3　generation.　Additionally,　the　accelerated　lifetime　of　the　Ti/blue-TiO2　-NTA/NATO　anode　was　increased　by　7　times　compared　to　the　Ti/NATO　anode.　When　combined　with　CNTs-C/PTFE　air　cathode　in　ORR-EO　system,　all　anodic　oxidation　and　O3　/H2　O2　processes　achieved　higher　center　dot　OH　production.　Over　92%　of　TOC　in　leachate　bio-effluent　was　effectively　eliminated　with　a　relatively　low　energy　cost　of　45　kWh/t.　(c)　2024　Published　by　Elsevier　B.V.　on　behalf　of　Chinese　Chemical　Society　and　Institute　of　Materia　Medica,　Chinese　Academy　of　Medical　Sciences.