The acyclic disiloxanes [CF(2)CH(2)OSiMe(3)](2) (1) and CF2[CF(2)CH(2)OSiMe(3)](2) (2) and the cyclic siloxanes [CF2CH2O](2)SiMe(2) (3), CF2[CF2CH2O](2)SiMe(2) (4), and [CF2CH2O](2)SiPh(2) (5) are synthesized by the reactions of the respective diols with hexamethyldisilazane or by the condensation reactions with silyl chlorides in the presence of triethylamine. Reactions of compounds 1-4 with C6F6, (CNF)(3), and CF3C(O)F are found to proceed readily in the presence of catalytic amounts of fluoride ion that liberate Me(3)SiF, Me(2)SiF(2), or Ph(2)SiF(2) to form cyclic and acyclic fluorinated ethers CC4F4COCH2(CF2)(2)CH2O (6), C6F5OCH2(CF2)(3)CH2OC6F5 (7), C6F5OCH2(CF2)(3)CH2OC6F5 (8), C3N3F2OCH2(CF2)(2)CH2OC3N3F2 (9), C3N3F2OCH2(CF2)(3)CH2OC3N3F2 (10), CF3C(O)CH2(CF2)(2)CH2C(O)CF3 (11), and CF3C(O)CH2(CF2)(3)CH2C(O)CF3 (12). 1 reacts with PhPCl(2) even in the absence of catalyst to form the cyclic phosphite (CF2CH2O)(2)PPh (13). The new compounds are characterized by spectral (IR, H-1 and F-19 NMR, MS) and analytical methods. The X-ray crystal structure of the bicylic ether 6 is determined. 6 crystallizes in the monoclinic system, space group P2(1)/n, with a = 9.393(3) Angstrom, b = 10.588(3) Angstrom, c = 11.110(4) Angstrom, beta = 111.42(2)degrees, V = 1028.7(5) Angstrom(3), d(calc) = 1.990 Mg m(-3), Z = 4, and R = 0.0351.