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Single-atom catalysts with full utilization of metal centers can bridge the gap between molecular and solid-state catalysis. Metal-nitrogen-carbon materials prepared via pyrolysis are promising single-atom catalysts but often also comprise metallic particles. Here, we pyrolytically synthesize a Co–N–C material only comprising atomically dispersed cobalt ions and identify with X-ray absorption spectroscopy, magnetic susceptibility measurements and density functional theory the structure and electronic state of three porphyrinic moieties, CoN4C12, CoN3C10,porp and CoN2C5. The O2 electro-reduction and operando X-ray absorption response are measured in acidic medium on Co–N–C and compared to those of a Fe–N–C catalyst prepared similarly. We show that cobalt moieties are unmodified from 0.0 to 1.0 V versus a reversible hydrogen electrode, while Fe-based moieties experience structural and electronic-state changes. On the basis of density functional theory analysis and established relationships between redox potential and O2-adsorption strength, we conclude that cobalt-based moieties bind O2 too weakly for efficient O2 reduction., Nitrogen-doped carbon materials with atomically dispersed iron or cobalt are promising for catalytic use. Here, the authors show that cobalt moieties have a higher redox potential, bind oxygen more weakly and are less active toward oxygen reduction than their iron counterpart, despite similar coordination.