At　the　molecular　level,　metal　coordinates　are　crucial　for　stabilizing　an　appropriate　electronic　configuration　for　high-efficiency　oxygen　reduction　reaction　(ORR)　electrocatalysts.　In　this　work,　an　excellent　platform　to　realize　the　decoration　of　Fe　coordinates　at　the　subnanometer　scale　into　nitrogen-doped　carbon　networks　(designated　as　Fe-Fe@NC)　is　provided.　X-ray　absorption　spectroscopy　confirmed　the　precise　configuration　of　Fe　coordinates　with　Fe-Fe　and　Fe-N　coordinations　at　the　molecular　level.　As　a　cathode　catalyst,　the　newly　developed　Fe-Fe@NC　exhibited　superior　ORR　performance　and　a　higher　peak　power　density　of　175　mW　cm-2　in　Zn-air　batteries.　Unlike　most　reported　pristine　Fe-based　catalysts,　Fe-Fe@NC　also　showed　good　oxygen　evolution　reaction　(OER)　activity,　with　a　low　operating　potential　(1.67　V　vs.　RHE)　at　a　current　density　of　10　mA　cm-2.　Calculations　based　on　density　functional　theory　revealed　that　the　Fe-Fe　coordination　in　Fe　subclusters　favored　the　4e-　transfer　pathway　and,　thus,　achieved　highly　active　catalytic　performance.　This　work　reveals　that　iron　clusters　at　the　subnanometer　scale　provide　an　optimized　electronic　structure　for　enhanced　ORR　activity.　©　2020　The　Royal　Society　of　Chemistry.