Since the discovery of high electrical conductivity in doped polyacetylene in 1977, π-conjugated polymers have emerged as viable semiconducting electronic materials for numerous applications. In the context of polymer electronic devices, one must understand the nature of the polymer surface's electronic structure and the interface with metals. For conjugated polymers, photoelectron spectroscopy—especially in connection with quantum-chemical modeling—provides a maximum amount of both chemical and electronic structural information in one (type of) measurement. Some details of the early stages of interface formation with metals on the surfaces of conjugated polymers and model molecular solids in connection with polymer-based light-emitting devices (LEDs) are outlined. Then a chosen set of issues is summarized in a band structure diagram for a polymer LED, based upon a “clean calcium electrode” on the clean surface of a thin film of poly(p-phenylene vinylene) (PPV). This diagram helps to point out the complexity of the systems involved in polymer LEDs. No such thing as “an ideal metal-on-polymer contact” exists. There is always some chemistry occurring at the interface.