As low-cost electrocatalysts for oxygen reduction reaction applied to fuel cells and metal-air batteries, atomic-dispersed transition metal-nitrogen-carbon materials are emerging, but the genuine mechanism thereof is still arguable. Herein, by rational design and synthesis of dual-metal atomically dispersed Fe,Mn/N-C catalyst as model object, we unravel that the O₂ reduction preferentially takes place on Fe^III in the FeN₄ /C system with intermediate spin state which possesses one e_g electron (t_2g4e_g1) readily penetrating the antibonding π-orbital of oxygen. Both magnetic measurements and theoretical calculation reveal that the adjacent atomically dispersed Mn-N moieties can effectively activate the Fe^III sites by both spin-state transition and electronic modulation, rendering the excellent ORR performances of Fe,Mn/N-C in both alkaline and acidic media (halfwave positionals are 0.928 V in 0.1 M KOH, and 0.804 V in 0.1 M HClO₄), and good durability, which outperforms and has almost the same activity of commercial Pt/C, respectively. In addition, it presents a superior power density of 160.8 mW cm⁻² and long-term durability in reversible zinc–air batteries. The work brings new insight into the oxygen reduction reaction process on the metal-nitrogen-carbon active sites, undoubtedly leading the exploration towards high effective low-cost non-precious catalysts.