Hydrogen　peroxide　(H2O2)　is　an　important　chemical　with　a　diverse　range　of　industrial　applications　in　chemical　synthesis　and　medical　disinfection.　The　traditional　anthraquinone　oxidation　process,　with　high　energy　consumption　and　complexity,　is　being　replaced　by　cost-effective　and　environmentally　friendly　alternatives.　In　order　to　explore　suitable　catalysts　for　the　electrocatalytic　synthesis　of　H2O2,　the　stability　of　B,N-doped　graphene　loaded　with　various　p-block　metal　(PM)　single　atoms　(i.e.,　PM-NxBy:　x　and　y　represent　the　number　of　atoms　of　N　and　B,　respectively)　and　the　effects　of　different　numbers　and　positions　of　B　dopants　in　the　second　coordination　shell　on　the　catalytic　performance　were　studied　by　density　functional　theory　(DFT)　calculations.　The　results　show　that　Ga-N4B6　and　Sb-N4B6　exhibit　enhanced　stability　and　2e−　oxygen　reduction　reaction　(ORR)　activity　and　selectivity.　Their　thermodynamic　overpotential　η　values　are　0.01　V,　0.03　V　for　Ga-N4B6’s　two　configurations　and　0.02　V,　0　V　for　Sb-N4B6’s　two　configurations.　Electronic　structure　calculations　indicate　that　the　PM　single　atom　adsorbs　OOH*　intermediates　and　transfers　electrons　into　them,　resulting　in　the　activation　of　the　O-O　bond,　which　facilitates　the　subsequent　hydrogenation　reaction.　In　summary,　Sb-N4B6　and　Ga-N4B6　exhibit　extraordinary　2e−　ORR　performance,　and　their　predicted　activities　are　comparable　to　those　of　known　outstanding　catalysts　(such　as　PtHg4　alloy).　We　propose　effective　strategies　on　how　to　enhance　the　2e−　ORR　activities　of　carbon　materials,　elucidate　the　origin　of　the　activity　of　potential　catalysts,　and　provide　insights　for　the　design　and　development　of　electrocatalysts　that　can　be　used　for　H2O2　production.　©　2024　by　the　authors.