A series of gold- and silver-containing ionic liquids, [C(n)MIM][M(CN)(2)] (M = Au, Ag; n = 12, 14, 18), prepared by metathesis reactions, present luminescence depending on their physical state i.e. crystalline or smectic A phases. The photoluminescent measurements as well as DFT calculations suggest that the modulation of aurophilic intermolecular interactions are responsible for this phosphorescent behaviour.