The homologous fluoride and hydroxide complexes of gold(III) [PPh₄][(CF₃)₃AuX] [X = F (1), OH (2)] have been structurally characterized by single-crystal X-ray diffraction methods. Both of them crystallize in the P2₁/n space group, yet they are not isomorphous. Despite the intrinsic difficulty to distinguish between F^- and OH^- by X-ray diffraction, the ability of the OH ligand in complex 2 to establish intramolecular O-H^...F hydrogen bonding with one of the CF₃ groups in cis position enables a clear differentiation from the fluoride complex 1. Given the tendency of late-transition metal fluorides to undergo hydrolysis, much caution should be taken when ascribing the identity of a fluoride ligand by X-ray diffraction methods, especially where unusual geometries are implied.