Novel poly(arylene ether)s with a rigid and zigzag 4,4''-o-terphenyldiyl structure, introduced into the polymer backbone were synthesized by nucleophilic displacement reaction of 4,4''-dihydroxy-o-terphenyl with several activated aromatic dihalides in virtually quantitative yields. The poly(arylene ether)s having high molecular weight show both good solubility in common organic solvents and high thermal stability up to 545 degrees C. They are amorphous with glass transition temperatures of 160-200 degrees C.