The dielectric relaxation of amorphous bulk poly(2, 6‐dimethyl phenylene oxide) (PPO) has been measured between −160° and 260°C over a frequency range extending from 0.1 to 10 kHz. Two broad loss peaks of comparable intensities are observed‐a high‐temperature &agr; relaxation identified with the glass transition and a low‐temperature &ggr; relaxation of uncertain origin. The intensity of the &agr; relaxation can be well accounted for in terms of a loss of orientational dipolar correlation in a calculation based on a consideration of a rotational isomeric model and of the geometry of the PPO chain.