We have prepared V2O3 thin films on Al 2O3 (0001) substrate by RF magnetron sputtering using oxygen radical and V-metal target, and studied their electronic structures by X-ray absorption spectroscopy (XAS) and X-ray photoemission spectroscopy (XPS). The as-deposited V2O3 thin films deposited at 600 °C exhibits high crystallization by oxygen radical irradiation during deposition. The electrical resistivity decreases with increasing deposition temperature, and this result is due to decreasing electron scattering. The crystal field splitting (10Dq) of the V2O3 thin film estimated from the fitting of the V 2p XAS spectrum is larger than that of the bulk crystal. In the XPS spectrum of the valence band region, the density of state (DOS) of the a1g orbital in the V 3d state increases at around the Fermi level. These results contribute to the lattice distortion between the thin film and the substrate.