Reaction of the ionic liquid [NEt3Me][Cl3] with white phosphorus (P4) gives, quantitatively, hexachlorophosphate [NEt3Me][PCl6]. This compound shows similar reactivity as PCl5, as confirmed for the reaction with phenol, carboxylic acids and ammonium chloride. At elevated temperature, [NEt3Me][PCl6] releases PCl3 and can therefore be used as a potential PCl3-storage material.