Ordered binary oxide films of vanadium oxide have been prepared on an aluminum oxide film supported on Mo(110) under ultrahigh vacuum conditions and characterized by various surface analytical techniques. Auger electron spectroscopy, low energy electron diffraction, high-resolution electron loss spectroscopy, x-ray photoelectron spectroscopy and ion scattering spectroscopy indicate that the vanadia films grow epitaxially on the Al2O(3)/Mo(110) surface as V2O3(0001). The results of electronic structural measurements show an increase in the energy of the a(1g) level in the 3d band at low temperatures, which is a possible explanation for the metal-to-insulator transition in V2O3