α,α,ω-Tri-H-perfluoroalkyl and phenyl 3-oxapolyfluoroalkanesulfonates XOCFaCFaO3R [R=HCFaCFaCHa,X=ICF₂CF₂ (1 a),CH₃(1b),Cl₂CFCF₂ (1c),HOF₂CF₂CH₂ (1d);R=H(CF₂CF₂)₂CH₂: X=Cl₂CFCF₂(1e);R=O₆H₅:X=CF₂CF₂ (1f); Cl₂CFCF₂ (1g)].were synthesized by the reactions of 3-ogaperfluoroalkanesulfonyl fluorides with 1,1,3-tri-H-tetraflnoropropanol,1,1,5-tri-H-perfluoropentanol and phenol respectively in 50-90% yields.The main factor affecting the yield,of the sulfonates was the reaction temperature,not the amount of base used.The sulfuroxygen and/or carbon-oxygen scissions can occur in these snlfona,tes during nucleophilic substitution.