Reactions of,4'-CF3C6F4OC6F4Li, generated in situ, with elements of group 16 (S, Se, Te) lead to CF3C6F4OC6F4SH (2), (CF3C6F4OC6F4Se)(2) (3), and (CF3C6F4OC6F3Te)(2) (4)/(CF3C6F4OC6F3)(2)Te (4a). The phenol derivative CF3C6F4OC6F4OH (1) is obtained by reaction of CF3C6F4OC6F4Li with B(OMe)(3)/H2O2. The reaction of CF3C6F4OC6F4Li with trimethylsilyl chloride or trimethyltin chloride gives CF3C6F4OC6F4XMe3 (X = Si (5), Sn (6). Oxidation of 2 in the presence of bromine results in the formation of (CF3C6F4OC6F4S)(2) (7) and CF3C6F4OC6F4SO2Br (8). Mixed perfluoroaryloxo/thio ethers CF3C6F4OC6F4SC6F4R (R = NO2 (9), CN (10), CF3 (11) and CF3C6F4OC6F4SC5F4N (12) are obtained upon reaction of 2 with excess C6F5R and pentafluoropyridine in the presence of K2CO3. With 4-C6F5OC6F4NO2, a mixture of (2-CF3C6F4OC6F4S)(4-C6F5O)C6F3NO2 (13) and 9 is formed. Reaction of. excess 2 with C6F5R gives the 2,4,6-substituted benzenes (CF3C6F4OC6F4S)(3)C6F2R (R = NO2 (14), CN (15)). The trimethylsilyl ether CF3C6F4OC6F4OSiMe3 tig) is prepared from the reaction of 1 with hexamethyldisilazane. 16 is a convenient reagent for the preparation of the aryl ethers CF3C6F4OC6F4OC6F4R (R = NO2 (17), CN (18) and CF3C6F4OC6F4OC6F4N (19) upon reaction with C6F5R and C5F5N The secondary alcohols CF3C6F4OC6F4CH(C6H5)OH (20) and CF3C6F4OC6F4CH(C6F5)OH (21) are synthesized by the reactions of 5 with benzaldehyde and pentafluorobenzaldehyde in the presence of tetrabutylammonium fluoride as a catalyst. In the synthesis of 21 the byproduct CF3C6F4OC6F4CH(C6F5)OC6F4CHO (22) is also formed and isolated.