Controlling the energy levels at the interface between an inorganic and an organic material is of importance to improve the properties in devices based on such hybrid interfaces, and can be obtained by the incorporation of dipole molecules between the materials. In this report interfaces containing TiO2, a dipole molecule (benzoic acid or 4-nitrobenzoic acid) and a polymer, poly(3-hexylthiophene) (P3HT) were investigated using high kinetic energy photoelectron spectroscopy. We could successfully measure through all materials in the fully assembled systems, and thereby experimentally quantify the dipole induced change in the energy level alignment of the polymer and the TiO2. (C) 2011 Elsevier B.V. All rights reserved.