Preparation of alkyl fluorides and carbonates via divergent dehydroxyfluorination and carbonation of alcohols with trifluoromethyl trifluoromethanesulfonate (CF₃SO₂OCF₃) is described. The reactions performed with BTMG in THF provided alkyl fluorides in good yields, whereas those of two different alcohols with Et₃N in DCM formed asymmetric carbonates in moderate to excellent yields. CF₃SO₂OCF₃ was demonstrated to be either a “F” or a “CO” reagent in the reactions by changing the base, allowing the selective construction of alkyl fluorides and carbonates from the corresponding alcohols with high efficiency. Notably, the fluorine-containing asymmetric carbonates that are difficult to synthesize by other methods were comprehensively prepared by this method, which would have great application potential in both academic and industrial fields.