The polyfluoro aromatic ethers C(6)F(5)CH(2)OR(F) [R(F) = CF3, C2F5, CF3CH2, CF(CF3)(2), C(CF3)(3), C(CF3)(2)(C6F5), C(CF3)(2)(OCH2CF3), C(C6F5)(2)(CF3)], (4-CF3CH2O)C6F4CH2OCH2CF3, and C6F5CH2OCF2CF2OCH2C6F5, were synthesized from C6F5CH2Br in the presence of CsF by reaction with the perfluoro carbonyl compounds COF2, CF3C(O)F, C6F5COF, (C6F5)(2)CO, (CF3)(2)CO, and (COF)(2); reaction with polyfluoro siloxanes CF3CH2OSi(CH3)(3) and C6F5OSi(CH3)(3); or reaction with polyfluoroalkoxides generated from the fluorinated silanes CF3Si(CH3)(3), C6F5Si(CH3)(3), and CF3CH2OSi(CH3)(3) reacting with the carbonyl compounds listed above. Single-crystal X-ray analysis of C6F5CH2OC(C6F5)(2)(CF3) is reported. Reactivities of the carbonyl substrates and the silicon-containing reagents are discussed as a function of the alkyl (aryl) substituents present.