Reaction of [{Au(C6X5)(2)}Ag](n) (X = Cl, F) with the crown thioethers 1,4,7-trithiacyclononane ([9]aneS(3)), 1,4,8,11-tetrathiacyclotetradecane ([14]aneS(4)), or 1,4,7,10,13,16,19,22-octathiacyclotetracosane ([24]aneS(8)) affords a series of heteronuclear Au-I/Ag-I compounds of stoichiometry [{Au(C6X5)(2)}Ag(L)(x)] (L = [9]aneS(3), x = 2 (1, 4); L = [14]aneS(4), x = 1 (2, 5); L = [24]aneS(8), x = 0.5 (3, 6)) formed via Ag-S bonds and Au center dot center dot center dot Ag contacts. X-ray diffraction studies of some of these complexes reveal different structural arrangements and nuclearity depending on the nature of the crown thioether ligand and on the presence or absence of aurophilic interactions. All the complexes are luminescent in the solid state but not in solution. Density functional theory calculations on representative model systems of complexes 2-4 and 6 were carried out to determine the origin of the electronic transitions responsible for their optical properties, which strongly depend on the nature of the perhalophenyl groups bonded to gold.