The electronic structure of thin films of the organic semiconductors copper and vanadyl (VO) phthalocyanine (Pc) has been measured using resonant soft X-ray emission spectroscopy and resonant inelastic X-ray scattering. For Cu-Pc we report the observation of two discrete states near E-P. This differs from published photoemission results, but is in excellent agreement with density functional calculations. For VO-Pc, the vanadyl species is shown to be highly localized. 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.