A process for preparing a fluorinated poly(arylene ether) comprising the repeating unit:
wherein n provides a molecular weight up to about 30,000 to 100,000, X represents one of following groups: none, ketone, sulfone, sulfide, ether, hexafluoroisopropylidene, αω-perfluoroalkylene, oxadiazole, and Y is 4,4′-(hexafluoroisopropylidene)-diphenyl, 4,4′-isopropylidene diphenyl, 3,3′-isopropylidene diphenyl, phenyl, or chlorinated phenol which process comprises reacting a bis(pentafluorophenyl) compound and a bisphenol or hydroquinone in the presence of a dehydrating agent and a polar aprotic solvent is disclosed. Polymers resulting from the process show good promise as new passive optic polymer waveguide materials.