Herein,a method for synthesizing various alkyl trifluoromethyl and alkyl bromodifluoromethyl ethers using carbono-fluoridothioates(R-OC(=S)F)as precursors has been described.Carbonofluoridothioates were obtained upon the reaction of an alcohol and S=CF2 generated via the decomposition of an SCF3 anion,and then selectively transformed into their corresponding trifluoromethyl and bromodifluoromethyl ethers upon changing the reaction conditions.This transformation has also been extended to the one-pot,two-step conversion of alcohols into alkyl trifluoromethyl ethers.A series of alkyl bromodifluoromethyl ethers has also been synthesized.These compounds open up a new avenue for the synthesis of a wide range of useful fluorinated products.In addition,this method is suitable for the late-stage introduction of trifluoromethyl ethers in complex small molecules.