The morphology and electronic structure of surface-segregated titanium oxides on Pt3Ti(111) are presented. Core level photoemission spectra at grazing emission reveal two states of oxidation: a dominant and reducible four-valent oxide together with a small amount of a three-valent oxide is produced by oxidation in 0 2 at and below 400°C; an irreducible three-valent oxide by oxidation in 02 at and above 450 °C. The ratio between the active four-valent and the inactive three-valent oxides decreases with increasing oxidation temperature. The probability for reduction by CO is almost unity for the Ti 4+ oxide, and the conclusion must be that the four-valent oxide plays an active role for catalytic reactions. Scanning tunneling measurements relate these observations to changes in the dispersion and nucleation of the oxide overlayer. The four-valent oxide grows as islands with remaining areas open for CO adsorption while the three-valent oxide spreads on and blocks the crystal surface. Photoemission spectra relate these dispersion effects to an electronic interaction between the Ti 3+ oxide and adjacent Pt atoms. The above observations are in accordance with the common picture of dispersion effects in titania-supported SMSI catalysts and prove that interfacial energies play a crucial role whether the dominant phase is metallic or an oxide.