Bis(4-fluoro-3-trifluoromethylphenyl)phenylphosphine oxide is synthesized and six new poly(arylene ether)s are prepared by nucleophilic displacement of the fluorine atom on the benzene ring by several diphenols under basic conditions. The products show very high glass transition temperatures of up to 252 degrees C and very good thermal stabilities of up to 490 degrees C for 5% weight loss. The polymers display very low heat release rates in the microscale combustion calorimeter test, suggesting good flame retardance. All polymers are soluble in a wide range of organic solvents. Transparent thin films cast from dichloromethane exhibit tensile strengths up to 54MPa, a modulus of elasticity up to 0.97GPa and elongation at break up to 47% depending on their exact repeating unit structures.