The reactions of the mercaptocarboxylic acids HOOC(CH2)nSH (n = 1, 2) with H[AuCl4] followed by treatment with PMe2Ph led to the (phosphane)gold thiolates [Au{S(CH2)nCOOH}(PMe2Ph)] [n = 1, (1) 2 (2)], which can act as metalloligands towards complex fragments of a second metal. Compounds 1 and 2 react with [Cp°2ZrMe2] (Cp° = C5EtMe4) to give the trinuclear Zr/Au complexes [Cp°2Zr{κ1O‐OOC(CH2)nSAu(PMe2Ph)}{κ2O,O′‐OOC(CH2)nSAu(PMe2Ph)}] [n = 1 (3), n = 2 (4)]. Complexes 1−4 were characterized by 1H, 13C, 31P NMR and IR spectroscopy. The crystal structure of 4 shows mono‐ and bidentate coordination of two metalloligands to one zirconocene fragment. In solution at room temperature 3 and 4 are dynamic, and the carboxylato groups alternate between the mono‐ and bidentate bonding modes. Complex 4 shows catalytic activity in the oxidation of PPh3 with O2. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)