The noble-gas atom xenon can bind fluorine atoms and form several stable compounds. We study the electronic structure of the xenon fluorides (XeFn, n=2, 4, 6) by calculating their ionization spectra using a Green’s function method, which allows one to treat many-body effects at a high level. Our focus is on the valence region and on the Xe 4d core hole. We observe a sensitive dependence of the spectra on the number of fluorine ligands. Systematic line shifts are uncovered and explained. In the Xe 5s and F 2s inner-valence regimes, from XeF2 to XeF6, the usefulness of the one-particle picture of ionization is found to become progressively worse. Moreover, adding the electronegative fluorine ligands seems to enhance—not suppress—the Auger decay of a Xe 4d core hole.