A commercial submicrometer BaTiO3 powder was analyzed using X-ray photoelectron spectroscopy. The analysis revealed the powder surfaces to be covered with a layer of physisorbed H2O and chemisorbed -OH ions. A BaCO3 residual not detected with XPS was shown to be present in the powder using X-ray diffraction, suggesting that the carbonate takes the form of discrete particles rather than of a continuous surface layer. A relaxed surface phase detected in previous XPS analyses of bulk BaTiO3 was also shown to be present. Depth profiling revealed the powder surfaces to be Ti-rich, confirming the presence of a phase, or phases, to stoichiometrically balance the barium carbonate.