A novel class of semifluorinated perfluorocyclohexenyl (PFCH) aryl ether homo/copolymers was successfully synthesized with high yield through the step-growth polymerization of commercially available bisphenols and decafluorocyclohexene in the presence of a triethylamine base. The synthesized polymers exhibit variable thermal properties depending on the functional spacer group (R). PFCH aryl ether copolymers with random and alternating architectures were also prepared from versatile bis-perfluorocyclohexenyl aryl ether monomers. The PFCH polymers show high thermal stabilities with a 5% decomposition temperature ranging from 359 to 444 degrees C in air and nitrogen atmosphere. These semifluorinated PFCH aromatic ether polymers contain intact enchained PFCH olefin moieties, making further reactions such as crosslinking and application specific functionalization possible. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 232-238