Our results suggest that the chemical "nobleness" of Au(111) is sufficient to explain its selectivity towards H 2 O 2 , even at a clean surface and without considering the presence of electrolyte ions. We find all steps that break the O-O bond have sizeable kinetic barriers and are thus prohibited, even though they are thermodynamically favored. This situation does not change under more reducing conditions. It is thus not the applied potential, but the underlying chemistry that drives here the ORR selectivity. Our study further highlights as key the kinetic competition between PCET and non-PCET steps that cannot be simply resolved via Brønsted-Evans-Polanyi scaling relations.