A series of pentafluorophenyl substituted ammonium, iminium, amidinium, and phosphonium halides are presented which show extensive anion-pi interactions. Hereby, the well-known anion-donor-pi-acceptor as well as "eta 6" anion-pi-complex type interactions are observed. The latter is supported by fixation of the anion on ton of the aromatic system through hydrogen bonding. This arrangement was investigated by theoretical methods showing a highly attractive anion-pi interaction. In addition an eta(2)-type coordination of the anions to only two C-atoms of the electron-deficient ring system is described.