Poly(aryl thioether)s (F-PTEs) containing 2,3,5,6-tetrafluoro-1,4-phenylene moiety and polar moiety, such as 1,3,4-ozadiazole, ether ketone, and amide groups, were synthesized by nucleophilic aromatic substitution reaction of aryl fluorides and 4,4'-thiobisbenzenthiol. F-PTEs were amorphous with good thermal properties including high glass transition temperature (T-g) and thermal stability, solubility, and hydrophobicity. F-PTEs were transformed into poly(aryl sulfone)s (F-PSs) by the oxidation reaction with hydrogen peroxide in acetic acid. Because of the sulfone group, the T(g)s of the F-PSs were 30-40 degrees C higher than those of the corresponding F-PTEs. F-PSs maintained solubility in polar aprotic solvents and exhibited hydrophobicity in spite of the content of polar sulfone groups due to the highly substituted fluorine atoms. These F-PTEs and F-PSs were a new class of high-performance polymers. (C) 2008 Wiley Periodicals, Inc.