The thermally stimulated depolarization current (TSDC) technique has been used to study the slow molecular mobility in the amorphous part of the semicrystalline polymer, poly(ethylene oxide) (PEO). Experiments were carried out in the temperature range that includes the glassy state, the glass transformation region and the rubber state. The dipole moments in the polymeric main chain originated a broad and low intensity secondary relaxation in the temperature region from −130°C up to the glass transition region; the activation energy of the motional modes of this secondary relaxation was in the range between 35 and 100 kJ mol−1. The glass transition temperature of the PEO, provided by the TSDC technique, was Tg = −53°C, and the fragility index was found to be m = 43. A strong relaxation above Tg was observed, whose molecular origin was discussed. The thermal behavior of the PEO was also characterized by differential scanning calorimetry.