Described herein are methods for the bromine-facilitated synthesis of fluoro-sulfur compounds, that include SF4, SF5Cl, SF5Br and SF6. The methods described herein generally require lower temperature and pressure, produce higher yields, require less time, do not use corrosive or costly reactants and solvents that are commonly used in the synthesis of the fluoro-sulfur compounds, and do not produce deleterious waste products when compared to previously-used methods.