A series of luminescent dinuclear gold(l) complexes with different crown ether pendants, [Al-2(Pboolean ANDP)(S-B15C5)(2)] [S-1315C5 = 4'-mercaptobenzo-15-crown-5, PAP = bis(dicyclohexylphosphino) methane (dcpm) (1), bis(diphenylphosphino) methane (dppm) (2)] and [Au-2((PP)-P-boolean AND)(S-B18C6)(2)] [S-B18C6 = 4'-mercaptobenzo-18-crown-6, (PP)-P-boolean AND = dcpm (3), dppm (4)], and their related crown-free complexes, [Au-2( PAP) (SC6H3(OMe)(2)-3,4)(2)] [PAP = dcpm (5), dppm (6)], were synthesized. The low-energy emission of the mercaptocrown ether-containing gold(l) complexes are tentatively assigned as originated from states derived from a S --> Au ligand-to-metal charge transfer (LMCT) transition. The crown ether-containing gold(l) complexes showed specific binding abilities toward various metal cations according to the ring size of the crown pendants. Spectroscopic evidence was provided for the metal-ion-induced switching on of the gold(...)gold interactions upon the binding of particular metal ions in a sandwich binding mode.