The　ever-growing　demand　for　hydrogen　peroxide　(H2O2)　makes　large-scale　production　via　environmentally-friendly　strategies　necessary.　The　electrochemical　oxygen　reduction　reaction　stands　out　as　an　efficient　and　green　approach　for　H2O2　production.　Here,　nitrogen-doped　mesoporous　carbon　materials　(NMCM)　with　a　hollow　semispherical　morphology　are　synthesized　for　H2O2　generation,　which　exhibit　remarkable　electrocatalytic　stability,　selectivity　(94.5%),　and　onset　potential　(~　0.6 V)　toward　the　H2O2　formation　in　neutral　environment.　The　distinct　H2O2　production　performance　of　NMCM　can　be　attributed　to　synergistic　effect　of　two　factors,　that　is,　the　pyrrolic　N　to　optimize　the　work　function　and　the　hollow　semispherical　morphology　to　facilitate　mass　transfer　and　expose　abundant　electrocatalytic　active　sites.　This　work　offers　a　facile　way　to　prepare　metal-free　electrocatalysts　for　realizing　high-performance　H2O2　production　in　neutral　solutions.　Graphical　Abstract:　Nitrogen-doped　mesoporous　carbon　materials　with　a　hollow　semispherical　morphology　and　high　pyrrolic　N　contents　are　synthesized　for　efficient　H2O2　production.　(Figure　presented.)　©　The　Author(s),　under　exclusive　licence　to　Springer　Science+Business　Media,　LLC,　part　of　Springer　Nature　2024.