The dielectric relaxation spectra of various poly(vinyl alcohol) (PVA)/glycogen blends and irradiated blend samples with 70 wt % PVA content that were undoped and doped with eosin were measured in extended temperature (30-160 degrees C) and frequency (1 kHz to 1 MHz) ranges. Dielectric relaxation spectroscopy separates different molecular groups of a repeating unit of a polymer with respect to the rate of its orientation dynamics. In the high-temperature range (>100 degrees C), the sigma relaxation, which is associated with the hopping motion of ions in the disordered structure of the biopolymeric material, can be measured. The electric dipole moment and the activation energy of the glass-transition temperature relaxation process were calculated. (C) 2008 Wiley Periodicals, Inc.