The interface between evaporated aluminum and poly(p‐phenylenevinylene) (PPV) was studiedinsituusing x‐ray photoelectron spectroscopy (XPS). PPV has potential for use in electroluminescent devices, and Al can be used as the electron‐injecting electrode. Aluminum was deposited on the PPV surface and the evolution of the chemical interactions at the interface was monitored using XPS. It was observed that the evaporated 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 &pgr; system of the polymer, which, based on the changes in the valence‐band spectrum, results in the disruption of the conjugation along the polymer chain in the near surface region. In contrast to recently published work by E. Ettedgui, H. Razafitrimo, K. T. Park, Y. Gao, and B. R. Hsieh [J. Appl. Phys.75, 7526 (1994)], no polymer band bending is observed. Shifts of the Al 2pmetallic peak as a function of coverage are attributed to cluster growth of the deposited film. ©1995 American Institute of Physics.