The evolution of the metal-polymer interface during the physical vapor deposition of Fe, Ni, Cu, Agr, and Au on poly(vinylchloride) (PVC) has been studied in situ using x-ray photoelectron spectroscopy. At low metal exposures, all of the metals studied reacted with PVC, forming a metal chloride. For those metals with more than one stable oxidation state, the salt produced corresponded to the metal's lowest stable oxidation state, e.g., CuCl instead of CuCl2. Higher metal exposures resulted in deposition of a metallic overlayer. For Fe, Ni, Cu, and Au. the variation in the metal's reactivity (measured by the metal/metal-chloride ratio as a function of metal coverage), was observed to increase in the order Feapproximate toNi>Cu>Au.