3-Trimethylsilyloxy-3'-vinylbiphenyl was treated with perfluorobenzene, substituted polyfluorobenzenes, and perfluoronaphthalene to give 4-[(per/polyfluoro)phenyloxy]-4'-vinylbiphenyls in the presence of catalytic amounts of CsF. The new monomers that resulted were characterized by mass spectra, H-1 and F-19 NMR, and IR spectroscopy. The new polymers obtained by polymerizing the monomers using AIBN-initiated free radical polymerization were characterized by gel permeation chromatography (GPC), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), H-1 and F-19 NMR and IR spectroscopies. The polymers were obtained as white powders and were soluble in all common organic solvents. They are thermally very stable and have high glass transition temperatures, T-g, i.e. >100 degrees C. Copolymerization of one of the monomers, 4-pentafluorophenyloxy-4'-vinylbiphenyl, 3, with different molar ratios of methylacrylate gave copolymers that have Low glass transition temperatures compared with the homopolymer of the monomer, 3, along with very high thermal decomposition temperatures, e.g. incorporation of even a small amount (2.1%) of 3 into the methylacrylate copolymer gave rise to a 50% char yield at 410 degrees C and a glass transition temperature of 28 degrees C.