The filled and unoccupied electronic states of the organic semiconductor copper-phthalocyanine (CuPc) have been determined by a combination of direct and resonant photoemission, near-edge X-ray absorption and first principles calculations. The experimentally obtained electronic states of CuPc are in very good agreement with results of ab initio density of states, allowing to derive detailed site specific information. (C) 2007 Elsevier B.V. All rights reserved.