Metal adhesion to polymers depends on the chemical structure at the interface. In the present work, we study the evaporation of Cr, Ti, and Au onto Teflon PFA (perfluoromethyl‐vinyl‐ether) substrates, and we modify the interface by post‐deposition x‐ray irradiation.Insitux‐ray photoelectron spectroscopy shows that deposition of reactive metals such as Cr and Ti leads immediately to crosslinking and to the formation of carbide and fluoride species. Less reactive metals, such as Au, cause only small loss of fluorine without formation of any new species. The metal/PFA interface is strongly affected by x‐ray irradiation in the case of Cr and Ti: remarkably enhanced crosslinking has been observed, which further increases with the metal coverage, while the carbides and fluorides remain basically unaffected. On the other hand, crosslinking increases only very slightly for pure PFA and for the Au/PFA interface, regardless of the Au thickness. These results suggest that radical recombination reactions are responsible for crosslinking at the interface between PFA and reactive metals.