Highly volatile and valuable reagents, perfluoroiodides were shown to complex with ionic liquids with the aid of a halogen-bond between a diverse set of anions and the electrophilic iodine atoms in perfluorinated iodides. The affinity of anions in various ionic liquids towards perfluoroiodides was examined by 19F NMR. Making use of the non-volatility of ionic liquids, we demonstrate here that perfluoroiodides can be stored and released controllably, on demand, from an ionic liquid matrix.