We report on a combined X-ray and UV photoemission spectroscopy study (XPS, UPS) of the interface between Poly(3-hexylthiophene) (P3HT) and mesoporous titanium dioxide (TiO2), a key element in the development of hybrid solar cells. We employed the elemental specificity of XPS to directly probe, on the complete P3HT/TiO2 heterostructure, the changes in the electronic levels alignment at the interface upon the addition of 4-Mercaptopyridine (4-MPy) molecules. We estimate an upper limit of 50 meV to the contribution of 4-MPy to the P3HT/TiO2 interfacial dipole. In addition, UPS was used to provide a quantitative estimate of the relevant parameters controlling the transfer of charge through the hybrid interface, such as the binding energy of the TiO2 valence and conduction bands and of the P3HT highest occupied/lowest unoccupied molecular orbitals. In both cases, we confirm that the alignment of P3HT energy levels to those of the substrate is not influenced by the position of the Fermi level inside the TiO2 band gap. (C) 2013 Elsevier B.V. All rights reserved.