A series of polyarylene ether nitriles were synthesized by the nucleophilic aromatic substitution polymerization of 2, 6-dichlorobenzonitrile with various bisphenol monomers. Owing to the different structural units, the derived copolymers showed different glass transition temperatures in the range of 166–260°C. Moreover, they all showed good film-forming properties and high mechanical strength ranging from 75MPa to 117MPa, and also exhibited high thermal stability with the 5% weight loss temperatures ranging from 373°C to 498°C. Furthermore, both the dielectric constant and dielectric loss were found to be relatively stable with respect to temperature before the turning point temperature, which is very near to the glass transition temperature.