A new method has been developed for the copper‐mediated trifluoromethylthiolation of allylic halides by using potassium fluoride, elemental sulfur, and (trifluoromethyl)trimethylsilane in anhydrous N,N‐dimethylformamide. This protocol provides facile access to a variety of allylic trifluoromethyl thioethers in moderate to good yields under mild, ligand‐free reaction conditions.

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A convenient process is described to convert a variety of allylic chlorides into allylic trifluoromethyl thioethers.

Aromatic‐, heteroaromatic‐, and aliphatic‐aldehydes can be used in the presented efficient method to yield the title products in good yields.