The electronic structure of the organic semiconductor vanadium oxide phthalocyanine has been studied using resonant inelastic X-ray scattering and X-ray emission spectroscopy. The vanadyl species in the films is shown to be highly localized, and good agreement between the measurements and a density functional calculation is obtained. Both dipole forbidden V 3d to V 3d*, and O 2p to V 3d* charge transfer transitions are observed, and explained in a local molecular orbital model. (c) 2005 Elsevier B.V. All rights reserved.