This work summarizes the miscibility and transport properties of different polymer blends obtained by mixing a bacterial, isotactic poly(3-hydroxybutyrate) (iPHB) with copolymers of styrene and vinyl phenol (Sty-co-VPh copolymers). Given that iPHB and pure commodity poly(styrene) (PS) form immiscible blends, PS has been modified by copolymerizing it with vinyl phenol (VPh) units, in an attempt to promote blend miscibility. VPh units have appropriate functional groups that interact with iPHB ester moieties. The potential miscibility was investigated by differential scanning calorimetry (DSC) measuring the glass transition temperatures of blends of different compositions. As an additional test. the interaction parameter between the two components, using the iPHB melting point depression caused by the second component, was also measured. Copolymers containing less than 90% styrene showed miscibility with iPHB. Given the remarkable barrier properties of iPHB to gases and vapours, the study has been completed by measuring transport properties of carbon dioxide through different iPHB/Sty-co-VPh copolymer blends, using gravimetric sorptions in a Cahn electrobalance. A clear difference was observed between the behaviour of rubbery blends and those that exhibit a glassy behaviour at the selected experimental temperature (303 K). (C) 2004 Elsevier Ltd. All rights reserved.