Five new poly(arylene ether)s containing phthalimidine group in the main chain and pendent trifluoromethyl group have been prepared by the reaction of 4,4'-(bis-4-fluoro-3-trifluoromethylphenyl)benzene (BTF) with bisphenols. Different molar ratios of N-phenyl-3,3-bis(4-hydroxyphenyl)phthalimidine (PA) and 4,4'-isopropylidenediphenol (BPA) have been used to generate different copolymers. The polymers obtained by step growth polymerization exhibited weight-average molecular weight upto 134,000 g/mol with a polydispersity index of 2.1-2.4. The homopolymer from BTF and PA showed very high glass transition temperature of 258 degrees C and outstanding thermal stability upto 536 degrees C for 5% weight loss under nitrogen. The polymers were Soluble in a wide range of organic solvents. Transparent thin films of these polymers exhibited tensile strengths upto 65 MPa and elongation at break upto 45% depending on the exact repeat unit structures. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 112: 1226-1233, 2009