The chemical and electronic properties of aluminum/poly(p-phenylenevinylene) (PPV) interfaces were studied in situ using x-ray photoelectron spectroscopy (XPS). It was observed that the aluminum atoms react with the oxygen-containing groups present as impurities on the surface of PPV to form Al-O-C linkages. The Al atoms also interact with the wrsystem of the polymer as indicated by changes in the valence band. Contrary to to recent suggestions (Ettedgui et al.) the relation between surface oxygen content and band bending is not straightforward, as shown by deposition on PPV surfaces prepared by two different synthetic routes.