Metal-coordinated nitrogen-doped carbons are highly active in promoting electrochemical oxygen reduction reaction (ORR). This study describes in detail the ORR kinetics on FeN 4 -graphene based on a density functional theory calculation. O 2 molecules chemisorbed on Fe site prefer hydrogenation into OOH species rather than direct breakage of the O–O bond. The subsequent reduction of OOH species into H 2 O 2 has a slightly high barrier (1.13 eV). However, this barrier could be bypassed by hydrogenation dissociation into O and H 2 O, which displays a low barrier (0.47 eV). Further O → OH and OH → H 2 O reactions are kinetically simple. Throughout the entire ORR, the initial O 2 → OOH reaction determines the total rate and displays a reaction barrier of 0.62 eV. This kinetic profile suggests that O 2 molecules are inherently favorable for reduction into H 2 O on FeN 4 -graphene following a four-electron process.