Hydrogen　peroxide　(H2O2),　a　green　oxidizing　agent,　is　extensively　utilized　across　diverse　industries,　including　wastewater　treatment　and　disinfection.　The　direct　electrochemical　synthesis　of　H2O2　via　the　two-electron　oxygen　reduction　reaction　(2e--ORR)　presents　a　sustainable　and　environmentally　friendly　alternative　to　the　conventional　anthraquinone　process,　which　suffers　from　high　energy　consumption　and　complex　multi-step　reactions.　In　this　study,　sulfur-doped　carbon　nanotube　materials　(S-CNTs)　were　successfully　synthesized　by　utilizing　sublimed　sulfur　as　the　sulfur　source　and　carbon　nanotubes　as　the　carbon　carrier,　heated　at　750　℃　in　an　H2/Ar　atmosphere　for　sulfurization　and　annealing.　For　comparison,　oxygen-doped　carbon　nanotubes　(O-CNTs)　and　pure　carbon　nanotubes　(CNTs)　were　also　prepared.　The　results　demonstrate　that　S-CNTs　catalysts　exhibit　outstanding　2e-ORR　performance　in　both　alkaline　and　neutral　environments.　In　alkaline　conditions,　the　selectivity　for　H2O2　exceeds　80%,　with　a　peak　value　of　93%　over　a　wide　potential　range　of　0.20～0.60　V　(vs.　RHE),　while　in　neutral　conditions,　the　selectivity　is　87%,　within　a　potential　range　of　0.20～0.50　V　(vs.　RHE).　Furthermore,　in　a　flow-cell　configuration　utilizing　commercial　RuIr@Ti　as　the　anode,　the　H2O2　yield　reached　6.16　mmol•cm−2•h−1　with　a　cumulative　concentration　of　30.8　mmol•L−1　under　alkaline　conditions,　while　under　neutral　conditions,　the　yield　was　5.82　mmol•cm−2•h−1　with　over　80%　Faradaic　efficiency.　The　incorporation　of　sulfur　into　the　carbon　nanotube　catalysts　effectively　modulated　the　coordination　environment　and　electronic　structure,　while　the　introduction　of　defect　sites　provided　an　ideal　active　center　and　robust　structural　foundation.　The　electronic　structure　modulation　of　the　carbon　substrate　and　the　enhancement　of　water　dissociation　via　sulfur-doped　carbon　nanotube　catalysts　not　only　significantly　reduced　the　reaction　overpotential　across　a　wide　pH　range　but　also　facilitated　the　production　of　high-concentration　hydrogen　peroxide,　thereby　improving　synthesis　efficiency.　This　study　offers　a　novel　and　cost-effective　approach　for　the　development　of　efficient　non-metal-doped　carbon　materials　as　electrocatalysts　for　the　two-electron　reduction　of　O2　to　H2O2　and　suggests　promising　applications　in　the　field　of　energy　and　environmental　technologies.　©　2025　Shanghai　Institute　of　Organic　Chemistry,　Chinese　Academy　of　Sciences.