X-ray absorption near-edge structure (XANES) is commonly used to probe the oxidation state of metal-containing nanomaterials; however, as the particle size in the material drops below a few nanometers, it becomes important to consider inherent size effects on the electronic structure of the materials. In this paper, we analyze a series of size-selected Pt_n/SiO₂ samples, using X-ray photoelectron spectroscopy (XPS), low energy ion scattering, grazing-incidence small-angle X-ray scattering, and XANES. The oxidation state and morphology are characterized both as-deposited in UHV, and after air/O₂ exposure and annealing in H₂. The clusters are found to be stable during deposition and upon air exposure, but sinter if heated above ∼150 °C. XANES shows shifts in the Pt L₃ edge, relative to bulk Pt, that increase with decreasing cluster size, and the cluster samples show high white line intensity. Reference to bulk standards would suggest that the clusters are oxidized; however, XPS shows that they are not. Instead, the XANES effects are attributable to development of a band gap and localization of empty state wave functions in small clusters.