A bicyclic pyrone-type species on oxygen-doped carbon catalysts was identified as the active site for the oxygen reduction reaction in acidic solution. It has much higher activity than that of typical nitrogen-doped carbon catalysts (0.219 e s-1 site-1vs. 0.021-0.088 e s-1 site-1 at 0.6 VRHE). The ortho-carbon atom in the carbonyl ring of the pyrone-type species was revealed as the reactive site by theoretical calculations.