Ti, Ag, and Au were evaporated onto Teflon PFA (polytetrafluoroethylene-co-perfluoroalkoxy vinyl ether) surfaces by electron beam evaporation. Au was also sputtered onto PFA, in order to examine the effect of the kinetic energy of the depositing metal atoms on the metal/polymer interaction. The evolution of metal/polymer interfacial structures with increasing deposited metal thickness was followed using x-ray photoelectron spectroscopy. It was found that Ti deposition leads to defluorination and the formation of fluoride and carbide species. The reactions increased with deposited Ti thickness, slowly in the initial stages of deposition but more rapidly afterwards. The effects of evaporated Ag and Au were very similar, both resulting in slight losses of fluorine : No formation of new species was detected. Compared to evaporated Au, sputtered Au increased polymer surface modification, indicated by the formation of -CF3, -CF-, and -C- species; an enhanced chemical reactivity was manifested by die appearance of Au fluorides. After deposition of the first several angstrom of metal, the rate of deposition onto the PFA was enhanced for evaporation but decreased for sputtering, due to the action of subsequently sputtered species.