The selective synthesis of a Au-I complex of 4-mercaptobenzoic acid, namely, [Au(SC6H4-4-COOH)(PMe2Ph)] (1), is reported. It shows interesting photoluminescence (PL) properties, for example, high PL quantum yield, multicomponent emission, and an unusually large PL lifetime. This complex was further applied as a metalloligand for the synthesis of [Cp*Zr-2{kappa O-1-OOCC6H4-4-SAu(PMe2Ph)}{kappa O-2,O'-OOCC6H4-4-SAu(PMe2Ph)}] (3), one of the rare Au-I/Zr-IV complexes. For the first time the exchange between the two ligands, which are bound in mono- and bidentate fashion, respectively, could be observed with the help of variable-temperature NMR spectroscopy. For the corresponding monometallic zirconocene complex [Cp*Zr-2(kappa O-1-O2CC6H4-4-SH)(kappa 2O,O'-O2CC6H4-4-SH)] (2) the activation parameters of this exchange could be determined by line shape analysis.