The organotin precursors 6‐Br‐Ace‐5‐SnBu3 (6, Ace = acenaphthyl) and 6‐Ph2E‐Ace‐5‐SnBu3 (7a: E = P; 7b: E = As; 7c: E = Sb) were prepared and used for the synthesis of organogold complexes, namely, the homodinuclear arylgold(I) species (6‐Ph2E‐Ace‐5‐Au)2 (8a: E = P; 8b: E = As; 8c: E = Sb), arylgold(III) dichloride 6‐Ph2P‐Ace‐5‐AuCl2 (9), diarylgold(III) chloride [trans‐(6‐Ph2P‐Ace‐5‐)2Au]Cl ([10]Cl), as well as the heterodinuclear gold complexes 6‐Ph2P(AuX)‐Ace‐5‐Au(AsPh3) (11a: X = Cl; 11b: X = Br). Compounds 8a ‐ 8c, 11a, and 11b show significant aurophilic interactions, which are related to their photoluminescence upon exposure to UV light. In the solid state, 11a and 11b show green‐yellow emission, whereas 8a ‐ 8c are non‐emissive. In solution under an argon atmosphere, all five compounds 8a ‐ 8c as well as 11a and 11b show green‐yellow emission. The organogold complexes were characterized by multinuclear NMR spectroscopy, photoluminescence spectroscopy, single‐crystal X‐ray crystallography, as well as (TD‐)DFT calculations including real‐space bond indicators derived from atoms‐in‐molecules (AIM), the electron localization indicator (ELI‐D), and the non‐covalent interaction (NCI) index.