The new [N(CH3)(4)][WSF5] salt was synthesized by two preparative methods: (a) by reaction of WSF4 with [N(CH3)(4)][F] in CH3CN and (b) directly from WF6 using the new sulfide-transfer reagent [N(CH3)(4)][SSi(CH3)(3)]. The [N(CH3)(4)](-) [WSF5] salt was characterized by Raman, IR, and F-19 NMR spectroscopy and [N(CH3)(4)][WSF5]center dot CH3CN by X-ray crystallography. The reaction of WSF4 with half an aliquot of [N(CH3)(4)][F] yielded [N(CH3)(4)][W2S2F9], which was characterized by Raman and F-19 NMR spectroscopy and by X-ray crystallography. The WSF5- and W2S2F9- anions were studied by density functional theory calculations. The novel [W2OSF9](-) anion was observed by F-19 NMR spectroscopy in a CH3CN solution of WOF4 and WSF5-, as well as CH3CN solutions of WSF4 and WOF5-.