Reaction of the polymeric alkynyl complexes (AuC2C6H4R)n (R = 4-NH2 and 3-NH2) with the diphosphine PPh2C6H4PPh2 in the presence of Cu+ ions gave two novel heterometallic aggregates [{Au3Cu2(C2C6H4R)6}Au3(PPh2C6H4PPh2)3](PF6)2 (R = 4-NH2 (2), 3-NH2 (3)). The compounds obtained were characterized by NMR spectroscopy and ESI-MS measurements. The solid-state structure of their 4-NMe2 congener 1 is reported. The complexes 1–3 reversibly react with strong (HSO3Me and HSO3CF3) acids to give the adducts [{Au3Cu2(C2C6H4-R)6*(R′SO3H)6}Au3(PPh2C6H4PPh2)3](PF6)2 (R = 4-NMe2 (4), 4-NH2 (5), 3-NH2 (6)) with six acid molecules bound to the amine groups of the alkynyl ligands. Composition and structure of the adducts were established using ESI-MS and multinuclear (31P, 1H and 1H-1H COSY) NMR spectroscopy. It was found that formation of these adducts results in crucial changes of luminescence characteristics of the complexes 1–3 to give substantial (ca. 100 nm) blue shift of the emission maxima and a sharp increase (about an order of magnitude) in luminescence quantum yield for 4-NR2 substituted derivatives. In the case of 3-substituted complex 3 the effect of adduct formation is much less pronounced and leads to blue-shift of emission maximum for 30 nm accompanied with a small drop in emission quantum yield. Computational studies have been performed to provide additional insight into the structural, electronic and photophysical properties of the starting complexes and their acid adducts. Interpretation of the photophysical effects induced by the adduct formation was suggested.