X-ray photoelectron spectroscopy (XPS) method has been used to study the effect of oxygen on the surface of a carbon support on the result of NO2 interaction with model systems prepared by evaporation of palladium on highly oriented pyrolytic graphite (HOPG). For Pd/HOPG samples with an atomic ratio [O]/[C] ≤ 0.0035, graphite oxidized with the destruction of its structure to a depth of 10–15 graphene layers. In this case, palladium particles remained in the metallic state and penetrated into the subsurface layer of the support due to the deep oxidation of the adjacent carbon atoms. At the atomic ratio [O]/[C] ≈ 0.01–0.02, the result of the interaction changed dramatically. In this case, the HOPG remained stable, and the palladium particles were oxidized to form an oxide. This finding explained the high stability of supported palladium catalysts prepared on Sibunit carbon supports in reactions of oxidation catalysis.