Iodoperfluoro-3-oxaundecylsulfonyl fluoride reacted with Cu, Zn, or Grignard reagent to produce the respective organometallic species, which was further reacted with halohydrocarbons 4-ClC6H4Br, 4-CH3C(O)C6H4Br, CH2=CHCH2Br, and CH3SiCl, to give derivatives of R(CF2)(8)O(CF2)(2)SO2F [R = 4-ClC6H4 (7), 4-CH3C(O)C6H4 (5), CH2=CHCH2 (3), and CH3Si (13)], in moderate yields. The compounds were characterized by NMR, infrared, and mass spectroscopy as well as elemental analyses. The addition product of trichlorosilane and 3 was reacted with sodium methoxide to give (12H,12H,13H,13H,14H, 14H-hexahydroperfluoro-3-oxatetradecyl methylsulfonate) trimethoxysilane, [(CH3O)(3)Si(CH2)(3)(CF2)(8)O(CF2)(2)SO3Me] (11).