Gold(III) fluorosulfate is found to be a good fluorosulfate ion acceptor. The tetrakis(fluorosulfato)aurate(III) ion, [Au(SO3F)4]-, is found in solid, crystalline materials of the composition M[Au(SO3F)4], with M=Cs, K, Li, NO, or ClO2. Their syntheses and vibrational spectra are discussed. Ionic formulation as M+[Au(SO3F)4]- is suggested. The ability of Au(SO3F)3 to accept SO3F- ions extends also to the system HSO3F-Au(SO3F)3. This system is investigated by electrical conductance measurements and by UV-visible, Raman, and NMR (19F and 1H) spectroscopy. Gold(III) fluorosulfate is thought to be monosolvated and acts as a moderately strong acid in HSO3F according to H[Au(SO3F)4]+HSO3F [Au(SO3F)4]-+H2SO3F+. © 1979, American Chemical Society. All rights reserved.