Homopolymers and copolymers of poly(arylene ether nitrile) (PAEN)-bearing pendant xanthene groups were prepared by the nucleophilic substitution reaction of 2,6-difluorobenzonitrile with 9,9-bis(4-hydroxyphenyl)xanthene (BHPX) and with various molar proportions of BHPX to hydroquinone (100/0 to 40/60) with N-methyl-2-pyrrolidone (NMP) as a solvent in the presence of anhydrous potassium carbonate. These polymers had inherent viscosities between 0.61 and 1.08 dL/g, and their weight-average molecular weights and number-average molecular weights were in the ranges 34,200-40,800 and 17,800-20,200, respectively. All of the PAENs were amorphous and were soluble in dipolar aprotic solvents, including NMP, N,N-dimethylformamide, and N, N-dimethylacetamide and even in tetrahydrofuran and chloro-form at room temperature. The resulting polymers showed glass-transition temperatures (T(g)'s) between 220 and 257 degrees C, and the T(g) values of the copolymers were found to increase with increasing BHPX unit content in the polymer. Thermogravimetric studies showed that all of the polymers were stable up to 422 degrees C with 10% weight loss temperatures ranging from 467 to 483 degrees C and char yields of 54-64% at 700 degrees C in nitrogen. All of the new PAENs could be cast into transparent, strong, and flexible films with tensile strengths of 106-123 MPa, elongations at break of 13-17%, and tensile moduli of 3.2-3.7 GPa. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci 121: 2788-2793, 2011