The present study describes a series of pentafluorobenzyl ammonium salts with two, three, or four C6F5 units in order to investigate simultaneous interactions of several perfluorinated arenes with anions in the crystalline state. Most of the structures show multiple anion-pi contacts. However, only 6 center dot 2HI reveals an effective encapsulation of the iodide ion by the aromatic units. For comparison, the structure of 4b is investigated because it offers two pi-systems with inverse charge distribution to a bromide anion. Only the electron-deficient pi-system of the pentafluorophenyl group interacts with the anion.