The　electrochemical　production　of　hydrogen　peroxide　via　the　two-electron　(2e(-))　oxygen　reduction　reaction　(ORR)　is　an　environmentally　friendly　method　and　is　expected　to　be　an　alternative　means　to　the　industrial　anthraquinone　process.　It　is　particularly　suitable　for　on-site　and　small-scale　H2O2　requirements.　The　development　of　earth-abundant　catalysts　with　high　activity　and　selectivity　toward　H2O2　is　highly　desirable　and　challenging.　Here,　we　have　prepared　Co3O4　with　tunable　oxygen　vacancies　(OVs)　and　strongly　coupled　it　to　nitrogen-doped　carbon　nanotubes　through　an　exsolution　strategy.　The　Co3O4　with　a　higher　OV　concentration　exhibits　a　higher　2e(-)　ORR　activity,　higher　H2O2　selectivity,　and　lower　H2O2　reduction　reaction　(H2O2RR)　activity　so　that　effectively　improving　the　production　rate　of　H2O2　(1.6　mol　peroxide/gcatalyst/h　at　0.0　VRHE)　in　acidic　media.　The　catalyst　is　also　used　as　a　cathode　for　the　electro-Fenton　process　and　degrades　up　to　80%　of　40　mg/L　of　rhodamine　B　solution　within　25　min.　Density　functional　theory　calculation　shows　that　the　*OOH　binding　energy　(Delta　G(*OOH))　could　decrease　on　increasing　the　numbers　of　OVs,　which　subsequently　benefits　the　protonation　of　*OOH　to　generate　H2O2.　(c)　2021　Elsevier　Ltd.　All　rights　reserved.