The interaction of monolayer coverages of pentacene with the root 3 x root 3 silver terminated Si(1 1 1) surface has been studies by high resolution core level and valence band photoemission spectroscopies. Core level Si 2p spectra reveal that there is only a very weak interaction between the pentacene and the underlying silicon, however, there is evidence of Fermi level movement. Valence band spectra acquired with both s and p polarised light indicate that for the surface coverages investigated, the molecular layers are oriented parallel to the plane of the surface. These results are in agreement with recent scanning tunneling microscopy (STM) studies which indicated that the pentacene molecules form highly ordered layers with the plane of the molecule parallel to the surface. Changes in the workfunction and Fermi level movements have been used to determine the energy level alignment at the interface. A 0.35 eV interface dipole forms between the pentacene and the silver terminated Si(1 1 1) surface within a two monolayer deposition. Photoemission measurements of the energy level alignment at the interface reveal that there is almost no barrier to charge injection from the conduction band of the semiconductor to the lowest unoccupied molecular orbital (LUMO) of the pentacene molecule. (c) 2005 Elsevier B.V. All rights reserved.