The molecular relaxation behaviour of isotactic polypropylene (iPP) exposed to gamma radiation in air to various absorbed doses (up to 700 kGy) has been investigated by dielectric loss (tan delta) analysis; the polar (mainly carbonyl and hydroperoxide) groups that were introduced by radiation-induced oxidation were considered as tracer groups. All relaxation zones (alpha, beta, gamma and delta in the order of decreasing temperature), between 25 K and melting temperature, were studied in the frequency range from 1 kHz to 1 MHz. The changes observed in the dielectric relaxation spectra were related to the modifications in the structural and morphological parameters attributed to exposure of the iPP samples to radiation. Wide-angle X-ray diffraction was used to investigate radiation-induced changes in the crystalline structure and degree of crystallinity, since the alpha relaxation is connected with this phase. Infrared spectroscopy and gel measurements were used to determine the changes in the oxidative degradation and the degree of network formation, respectively. Conclusions derived using different methods were compared. This study reveals high dielectric and/or relaxation sensitivity of iPP to gamma radiation. Disappearance of the low-temperature dielectric (gamma and delta) relaxations together with large changes in intensity, position and activation energy of the dielectric alpha relaxation are observed with gamma irradiation and are mainly connected with oxidative degradation in iPP structure.