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Graphene coatings have been widely considered as protection layers on metal surfaces to prevent surface oxidation and corrosion in gaseous atmospheres. Here, using in-situ ambient pressure X-ray photoelectron spectroscopy we demonstrate that oxygen intercalation readily occurs at full monolayer graphene/Ru(0001) interfaces in 0.5 Torr O 2 around 150°C, resulting in decoupling of the graphene overlayer from the Ru surface and oxidation of the metal surface. Moreover, oxygen intercalation has been observed even upon illumination of the graphene/ Ru(0001) surface with an infrared lamp in air. These results indicate that the stability of graphene/metal interfaces under ambient conditions should be taken into consideration for future applications.