The metal-free phthalocyanine interface formation on rutile TiO2(110) is investigated using scanning tunneling microscopy and photoelectron spectroscopy. The molecules are adsorbed flat on the surface, centered on the substrate oxygen rows. High-resolution core-level C1s spectroscopy indicates a strong difference between the second layer and the first monolayer bonding to the surface. The C1s core-level from the second layer has a bulk-like line shape whereas the first layer shows a strongly modified line profile. Upon thermal treatment, changes in the N1s core level line profile points to dehydrogenation of the center of the molecule. (c) 2006 Elsevier B.V. All rights reserved.