The heteropolynuclear complex [Tl{Au(C6Cl5)2}]n reacts with sterically demanding diamines as tetramethylenediamine (TMDA), 2,2′-(ethylenedioxy)bis(ethylamine) (NOON), or triethylenetetramine (trien) in 1:1 molar ratio in tetrahydrofuran (THF), leading to products of stoichiometry [Tl{Au(C6Cl5)2}(L)]n (L = TMDA (1), NOON (2), or trien (3)) or [Tl2{Au(C6Cl5)2}2(L)]n (L = trien (4)) when the solvent used is toluene. Addition of acetylacetone to the diamine complexes in 1:1 molar ratio generates [Tl{Au(C6Cl5)2}{O═C(CH3)CHC(CH3)NH(CH2)4NH2}]n (5) and in 1:2 molar ratio [Tl{Au(C6Cl5)2}(Lx)]n (Lx = {O═C(CH3)CHC(CH3)NHCH2CH2}2 (6), {O═C(CH3)CHC(CH3)NHCH2CH2OCH2}2 (7)). When the molar ratio is 1:2, with the exception of 3, all these complexes display luminescence in the solid state at room temperature and at 77 K. The origin of the luminescence could be assigned to a delocalizated exciton along the heterometallic chain formed by Au···Tl interactions. In addition, a red shift is observed when the temperature decreases, which is attributed to the shortening of the Au−Tl distance at lower temperatures. The emissive properties of solutions of 5−7 and [Tl{Au(C6Cl5)2}]n in THF were studied after adding increasing amounts of different metal ions (Zn2+, Cd2+, Hg2+, Pb2+, Cu2+, Al3+, Ni2+, Ag+, Mn2+, Bi3+) and anions (F−, Cl−, Br−, I−, H2PO4−, ClO4−, Bz−, Ac−, HSO4−, NO3−). Interestingly, an enhancement of the fluorescence emission intensity was observed for the complexes considered only upon addition of Br−, Cl−, and Ac−.