The synthesis of 5-[(pentafluorosulfanyl)methyl]-2-oxazolines is reported. The use of a silver promoter allows the intramolecular cyclization of N-[2-chloro-3-(pentafluorosulfanyl)propyl]amide to occur without elimination of the chlorine atom, a reaction pathway typically observed for β-chloro-SF5-alkyl compounds. The products, potentially valuable SF5-containing heterocycles, are obtained in up to 97% yield.