We have studied the interface formed on a poly(p-phenylene vinylene) (PPV) thin film by deposition of a thermally evaporated aluminum layer. The cross-section of Al-coated PPV films was analysed by analytical transmission electron microscopy and complemented by X-ray photoelectron spectroscopy. The subsequent presence of oxygen was detected at the polymer-metal boundary accompanied by modified aluminum and carbon bonding states indicating chemical interaction between the metal and the polymer has occurred. The PPV structure was also affected by the evaporation process by the formation of a sublayer in the polymer bulk beneath the interface which reveals the presence of carbonyl groups and possible reticulation of carbon. It was suggested that the interaction between aluminum and carbon was initiated from the binding of the metal atoms to the oxygen of the observed sublayer.