Designing　atomically　dispersed　non-precious　metal　catalysts　for　2e(-)　oxygen　reduction　reaction　(ORR)　is　an　appealing　strategy　to　harness　O-2-to-H2O2　chemistry.　Nevertheless,　prevailing　M-N-C　single-atom　catalysts　(SACs)　might　still　not　satisfy　the　directional　regulation　of　ORR　selectivity,　hence　fail　to　uphold　scalable　H2O2　electrosynthesis　with　a　high　yield.　Herein,　we　report　the　precise　synthesis　of　(O,N)-coordinated　Fe　SAC　(FeN2O2)　and　relating　investigation　of　its　performance　in　H2O2　production　over　a　wide　pH　range,　in　comparison　with　the　FeN4　counterpart.　Density　functional　theory　simulations　reveal　that　the　coordination　chemistry　engineering　has　a　profound　influence　on　the　strength　of　the　oxygen　intermediate　adsorption.　The　electron　delocalization　of　M-O　configuration　readily　lowers　the　d-band　center　of　the　Fe　metal,　which　is　beneficial　to　weakening　the　intermediate　adsorption　capability　and　promoting　the　2e(-)　ORR　process.　The　thus-derived　FeN2O2　exhibits　impressive　selectivity　in　a　wide　pH　range,　particularly　reaching　95%　in　alkaline　conditions.　Furthermore,　our　designed　gas-diffusion　electrode　enables　a　favorable　H2O2　yield　(300　mmol　L-1)　at　a　current　density　of　60　mA　cm(-2)　for　50　h.　This　work　is　anticipated　to　inspire　the　rational　design　of　definitive　SAC　architecture　for　practically　feasible　electrochemical　production　of　H2O2　toward　environmental　remediation.