Reaction of the heterometallic complex [{Au(C6F5)(2)}Tl](n) with the quinoline pendant arm derivatives L-1 and L-2 of the mixed donor macrocycles [12]aneNS(2)O and PhenNS(2) affords the new Au(I)/T1(I) complexes [{Au(C6F5)(2)}Tl(L-1)] (1), [{Au(C6F5)(2)}Tl-(L-2)] (2), [{Au(C6F5)(2)Tl}{Au(C6F5)(2) Tl(L-1)}](2) (3), and [{Au(C6F5)(2)Tl}{Au(C6F5)(2)Tl(L-2)}](n) (4) depending on the reaction molar ratios used. These complexes present different optical properties strictly related to their structural features and to the presence of Au(I)center dot center dot center dot Tl(I) metallophilic interactions, which are finely tuned by the coordinating quinoline moiety and have been studied experimentally and theoretically via TD-DFT calculations.