By means of full atomistic molecular dynamics simulation, the solubility parameters for pure poly(3-hydroxybutyrate) and poly(ethylene oxide) are calculated and the results are in agreement with the literature values. Furthermore, in order to reveal the blend property, the volume-temperature curve of the PHB/PEO blend system (1:2 blends in terms of repeated units) is simulated by employing the united atom approximation to obtain the glass transition temperature. From the volume-temperature curve, the glass transition temperature is about 258 K, which is compared well with the experimental results. It should be pointed out that the two simulated solubility parameters are similar and there is only one glass transition of the blend system, these indicate that the studied blend system is miscible. (C) 2003 Elsevier Ltd. All rights reserved.