We have investigated the nature of the interaction between pentacene and Cu(110) for films grown by two different methods, and the energy level alignment at the resulting pentacene/Cu(110) interface. The first film was grown in a stepwise fashion at room temperature while the second film was grown using an annealed monolayer to template the growth of the subsequent layers. Synchrotron based photoemission techniques have been used to compare the initial stages of the growth of the two films. A thorough examination of the growth of both films indicates a strong bond between the initial monolayer of pentacene and the Cu(110) substrate, in addition to a change in molecular orientation for subsequent layers after the completion of the initial monolayer. A comparison of the two films indicates identical film growth for both films with the film templated by the annealed monolayer exhibiting a more uniform growth mode for the film thicknesses investigated. (c) 2006 Elsevier B.V. All rights reserved.