A one pot room temperature synthesis of thionyl tetrafluoride (SOF(4)) from elemental fluorine (F(2)) and thionyl fluoride (SOF(2)) is reported. The selective decagram scale process (100 mmol) allows a quantitative preparation of SOF(4) with high purity. The solid-state structure has also been elucidated and compared with the reported gas phase one. The use of this reagent for the formation of the emerging pentafluorooxosulfate [cat][OSF(5)] anions led to the preparation of multiple ion-pairs (cat=Ag, NEt(3)Me, PPN, PPh(4)) in different organic solvents. The SuFEx reservoir ability of this anion was studied and by tuning the solvent system, the reactivity of pure thionyl tetrafluoride was observed using Ag[OSF(5)] in THF and acetone.