The glass transition and the crystallinity of blends of isotactic bacterial PHB and low molecular mass atactic R, S-PHB-diols was investigated by means of differential scanning calorimetry (DSC), temperature-modulated DSC and dielectric spectroscopy. It was found that (i) T-g of crystallized blends is much lower than T-g of quenched blends, (ii) the semi-crystalline blends can only be described with a three-phase model. From the experimental results the amount of the oligomer component in the mobile amorphous as well as in the rigid amorphous phase was determined. It could be shown that the low molecular mass atactic R, S-PHB-diol is enriched in the mobile amorphous phase of the semi-crystalline blends, but 5-15% oligomer remains, however, in the rigid amorphous phase. (C) 2003 Elsevier Ltd. All rights reserved.