A series of poly(2‐alkyl‐6‐phenylphenylene ether)s were prepared by the oxidative polymerization of 2‐alkyl‐6‐phenylphenols. Their dielectric constants were approximately 2.5, whereas it was found that the phenyl group at the 6‐position clearly increased the Q factor of the polymer compared with poly(2,6‐dimethylphenylene ether), PPE. These values were qualitatively predicted from the polarizability and the molar volume calculated by the theoretical analysis of the unit structure at the HF/6‐31G* level.
