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Auger and X-ray photoelectron spectroscopies have been used to study the surface composition of MnxCo1-xO (0 ≤ x ≤ 1) solid solutions. The polycrystalline materials, which are bulk homogeneous, present clear signs of deviation in surface composition at xbulk ≈ 0.2–0.4 to become surface-enriched in manganese at the expense of the cobalt. Whether on stoichiometric or cobalt-depleted surfaces, cobalt retains the characteristic XPS 2p satellite structure and binding energies of the rock salt monoxide (CoO or MnxCo1-xO) environment. Manganese 2p XP spectra are appropriately monoxide-like for the stoichiometric surfaces but broaden and give evidence for a second manganese species with Mn4+ character for the bulk-enriched samples. Oxygen O 1s spectra also show two different surface species, one the characteristic rock salt lattice oxide at 529.4 eV and a second at 531.3 eV. However, the two peaks are observed for all samples, regardless of whether the surface and bulk compositions were found to differ. The second O 1s peak cannot be unequivocally identified, but is most likely defect-oxide or hydroxyl-like in origin. The 531.3-eV O 1s species forms at the expense of the lattice oxide, and the net oxide-surface concentration is approximately that of the stoichiometric surface.