Photoelectron spectroscopy (XPS and UPS) was used to study the deposition of metal layers (Phi(Ag), Phi(Cu), and Phi(An)) onto pentacene films. Very low work functions were measured N)Ag = 3.91 eV, (Phi(Cu) = 3.93 eV, and (Phi(Au) = 4.3 eV) for all of the metals, in agreement with results from the literature. The intensities of the C 1s core-level signals from pentacene that were monitored during stepwise metal deposition leveled off at a value of about 30% of a thick pentacene film. This C 1s intensity is comparable to that of one monolayer of pentacene deposited onto the respective metal. The valence band spectra of metals deposited onto pentacene and spectra collected for pentacene deposited onto bare metal surfaces are very similar. These findings lead to the conclusion that approximately one monolayer of pentacene is always present on top of the freshly deposited metal film, which explains the very low work function of the metals when they are deposited onto organic films. We expect similar behavior with other nonreactive metals deposited onto stable organic layers.