Thermally stimulated depolarization current is applied to study the dielectric relaxations coexisting from 80 to 380 K in the PLLA/starch, immiscible biodegradable blend system. The relaxation parameters are determined for chain mobilities at different ranges, whether in the amorphous or cold-crystallized state for PLLA, and totally amorphous one for starch as demonstrated by wide-angle X-ray scattering experiments. The PLLA crystallization is favored by the presence of starch, in both the crystallinity degree reached and the crystallization time. The effect of moisture is followed for both the local modes and the segmental mobilities, where a bimodal relaxation for starch sweeps the temperature range, thus evidencing the heterogeneities existing in the starch disordered phase. The moisture plasticization effect is estimated and shows differences in the water absorption in starch either neat or as a minority component. The onset of the segmental mobility in PLLA is independent of composition or crystallinity, but the large intensity decrease observed when PLLA cold-crystallizes evidences the simultaneous formation of a rigid amorphous fraction and the crystallites. The normal relaxation mode is recorded in amorphous PLLA whether neat or blended, which again demonstrates the absence of interactions among the blend components. (c) 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 680-691