A series of dinuclear diphosphine complexes of gold(I) alkynyls containing bis(diphenylphosphanyl)ethane/propane and alkynyl ligands with aromatic substituents (biphenyl, pyrene, and azobenzene) was synthesized and characterized using X-ray crystallography and NMR spectroscopy. Photophysical parameters of the compounds obtained strongly depend on the nature of aromatic substituents in the alkynyl ligands. Azobenzene containing derivatives are non-luminescent, whereas biphenyl and pyrene containing complexes display moderate emission both in solution and in solid state. The complexes with biphenyl substituents display strong heavy atom effect and show typical phosphorescent emission. In contrast, the complexes containing pyrene chromophore are fluorescent that points to the absence of spin orbit coupling in these systems, which additionally display static excimer emission in solid phase due to ground state π-stacking of the pyrene moieties.