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A new 2,7,10,15-tetraethynyldibenzo[g,p]chrysene ligand (<b>1</b>) and two tetranuclear gold(I) derivatives containing PPh₃ (<b>3</b>) and PMe₃ (<b>4</b>) phosphines were synthesized and characterized by ¹H and ³¹P NMR, IR spectroscopy, and high-resolution mass spectrometry. The compounds were studied in order to analyze the effect of the introduction of gold(I) on the supramolecular aggregation and photophysical properties. Absorption and emission spectra displayed broad bands due to the establishment of &#960; &#960; interactions as an indication of intermolecular contacts and the formation of aggregates. A decrease of the recorded quantum yield (QY) of the gold(I) derivatives was observed compared to the uncomplexed ligand. The introduction of the complexes into poly methyl methacrylate (PMMA) and Zeonex 480R matrixes was analyzed, and an increase of the measured QY of <b>4</b> in Zeonex was observed. No phosphorescent emission was detected.