The Lewis acidity of perfluorinated trimethylgold (CF₃)₃Au was assessed by theoretical and experimental methods. It was found that the (CF₃)₃Au unit is much more acidic than its nonfluorinated analogue (CH₃)₃Au, and probably sets the upper limit of the acidity scale for neutral organogold(III) species R₃Au. The significant acidity increase on fluorination is in line with the CF₃ group being more electron-withdrawing than CH₃. The solvate (CF₃)₃Au⋅OEt₂ (1) is presented as a convenient synthon of the unsaturated, 14-electron species (CF₃)₃Au. Thus, the weakly coordinated ether molecule in 1 is readily replaced by a variety of neutral ligands (L) to afford a wide range of (CF₃)₃Au⋅L compounds, which were isolated and characterized. Most of these mononuclear compounds exhibit marked thermal stability. This enhanced stabilization can be rationalized in terms of substantially stronger [Au]−L interactions with the (CF₃)₃Au unit. An affinity scale of this single-site, highly acidic organogold(III) fragment was calculated by DFT methods and experimentally mapped for various neutral monodentate ligands. The high-energy profile calculated for the fluorotropic [Au]−CF₃⇌F−[Au]←CF₂ process makes this potential decomposition path unfavorable and adds to the general stabilization of the fragment