Human　life　relies　on　hydrogen　peroxide　(H2O2),　which　is　a　crucial　chemical.　H2O2　can　be　produced　via　electrochemical　methods　using　two-electron　oxygen　reduction　reaction　(2e−　ORR)　on　atomically　dispersed　catalysts,　making　it　a　promising　substitute　for　the　traditional　anthraquinone　process,　but　still　has　lenty　of　room　for　optimization.　Axial　coordination　regulation　of　active　sites　is　a　potential　means　to　improve　the　selectivity　of　2e−　ORR.　Herein,　we　design　twenty　types　of　single　atom　sites　with　precisely　defined　M–N4–C　moiety　functionalized　by　axial　coordination　R　(R=Cl,　Br).　By　calculation　of　density　functional　theory　(DFT),　different　from　pristine　M–N4–C　moiety,　Cl–Cu–N4　and　Br–Zn–N4　especially　Br–Zn–N4　has　the　most　favorable　2e−　ORR　catalytic　efficiency　with　the　overpotential　of　0.07　and　0.05　V,　respectively.　In　addition,　the　Gibbs　free　energy　of　the　intermediate　O*　exceeds　3.52　eV,　indicating　a　significant　suppression　of　the　competitive　4e−　ORR　reaction.　Electronic　analyses　show　that　the　axial　Br　in　Zn–N4–Br　can　optimize　the　3D　orbital　of　Zn　center　to　enhance　O2　adsorption　and　activation　at　Zn　site,　thus　reducing　ORR　barrier　and　accelerating　ORR　kinetics.　This　work　extends　the　field　of　view　of　adjusting　the　reaction　path　of　monatomic　electrocatalysis　through　axial　coordination　engineering.　©　2023