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Scanning photoelectron spectromicroscopy has been used to study the onset and the initial stages of oxidation of Ru(0001) at three oxidation temperatures, 625, 675, and 775 K, and oxygen exposures of about 105 Langmuir. The lateral heterogeneity developed during oxide nucleation and growth and the local composition of the coexisting phases have been determined using as fingerprints the O 1s and Ru 3d spectra, thus combining chemical mapping with spectroscopy from selected features from the maps. The onset of oxide formation is characterized by the appearance of randomly distributed small islands (⩾0.5 μm) identified as germinal patches exhibiting some spectral features of bulk RuO2. The following anisotropic growth of the RuO2 phase and in particular the shape of the oxide islands shows a strong dependence on the oxidation temperature. The spectroscopic information obtained for the areas surrounding the oxide islands reveals an intermediate oxygen state characterized by distinct O 1s and Ru 3d features different from both the chemisorbed and the oxide form. It is assigned to an intermediate state acting as precursor of the oxide. The experimental data are discussed in the framework of the oxidation pathway and of core level fingerprints for the various oxygen–Ru phases suggested in recent theoretical models.