The energy level alignment of vacuum deposited molecular films of tetrafluorotetracyanoquinodimethane (F4-TCNQ) on various substrates has been studied by photoelectron spectroscopy. The interfaces studied span the work function range from 3.45 to 5.8 eV. In this range, the Fermi level of the substrate is pinned in proximity to LUMO level. This indicates that a charge transfer mechanism is responsible for the observed alignment scheme. The photoelectron emission study of sub-monolayer of F4-TCNQ revealed presence of electrons in the charge transfer states at the interface. In this context the electronic structure of neutral and negatively charged F4-TCNQ has been studied theoretically and by photoelectron spectroscopy. (c) 2007 Elsevier B.V. All rights reserved.