Barbier-type reactions of ICF2CF2OCF2CF2SO2F, I(CF2CF2)4OCF2CF2SO2F, and I(CF2CF2)4OCF(CF3)2 with MeMgBr and ClSiMe3 in 3:1 tetrahydrofuran (THF)/diethyl ether mixtures at −78 °C gave Me3SiCF2CF2OCF2CF2SO2F (1), Me3Si(CF2CF2)4OCF2CF2SO2F (2), and Me3Si(CF2CF2)4OCF(CF3)2 (3) in 65−89% yields. The anions in three difluorometalates, [(Me2N)3S]+[Me3SiF2]- (TASF), [Bu4N]+[Me3SiF2]- (TBAT), and [(Pip2N)3S]+[Me3SnF2]- (TPSF), were reacted with 1−3, to generate 2 equiv of Me3SiF for TASF and TBAF or 1 equiv each of Me3SnF and Me3SiF for TPSF, and the perfluoroalkyl ether nucleophiles -CF2CF2OCF2CF2SO2F, -(CF2CF2)4OCF2CF2SO2F, and -(CF2CF2)4OCF(CF3)2, respectively. The sulfonium or ammonium countercation interacted with hexafluorobenzene, monosubstituted pentafluorobenzenes, and pentafluoropyridine over a range of temperatures between −78 and 25 °C to also generate aryl carbocationic species that reacted with -CF2CF2OCF2CF2SO2F to give XC6F4CF2CF2OCF2CF2SO2F, where C−X = C−F (4), C−NO2 (5), C−CN (6), C−CF3 (7), C−CHCH2 (8), N (9), with -(CF2CF2)4OCF2CF2SO2F to give XC6F4(CF2CF2)4OCF2CF2SO2F, where C−X = C−NO2 (10), C−CN (11), C−CF3 (12), N (13), and with -(CF2CF2)4OCF(CF3)2 to give XC6F4(CF2CF2)4OCF(CF3)2, where C−X = C−F (14), C−NO2 (15), C−CN (16), C−CF3 (17), C−CHCH2 (18), N (19). The new products were obtained in 22−73% yields, and purification was carried out by separation of fractions either by silica gel preparative thin-layer chromatography (TLC) by using a diethyl ether/cyclohexane mixture as the mobile phase eluent (XC6F4(CF2CF2)4OCF(CF3)2 type compounds) or by octadecyl bonded reverse-phase thin-layer chromatography (rp-TLC) by using an acetonitrile/water mixture as eluent. Reaction of compound 16 with 2 mol equiv of Me3SiOOCMe resulted in the disubstitution product at ortho positions of the nitrile. Compound 5 was transformed via a five-step process to the tricarboxylate o-(MeCOO)2O2NC6F4CF2CF2OCF2COOMe (24). The new products were characterized by elemental analyses and NMR and high-resolution mass spectral analysis.