The normal reaction product of 3-oxa-5-iodoperfluoropentanesulfonyl fluoride (1) with potassium sulfite in aqueous solution was the corresponding potassium sulfinate 2, but when the reaction was carried out in aqueous diogane, potassium 3-oxa-1, 6-perfluoropentane disulfinate(8), was formed instead of 2.The optimal condition for the preparation of 3(90% yield) was stirring at 70~80℃ for several hours with a molar ratio of the reducing agent to the substrate of ≥3:1, 3-Oxa-7-iodoperfluoroheptane-sulfonyl fluoride (6) and 1, 4-diiodoperfluorobutane (6) were similarly converted into the corresponding disulfinate 7 and 8 respectively. We suggest the name deiodosulfination for this radical reaction which can also be carried out in diglyme or THF but not in DMF, pyridine or triethylamine.