In this study, the effect of composition and melting time on the phase separation of poly(3-hydroxybutyrate)/poly(propylene carbonate) (PHB/PPC) blend thin films was investigated. Optical microscopy under phase contrast confirms the occurrence of phase separation of PHB/PPC blends at 190 degrees C. Polarized optical and scanning electron microscopies (POM and SEM) demonstrate that phase separation takes place along both horizontal and vertical film planes, which should be attributed to the two different interfaces and immiscible blends. A low PPC content (e.g. 30 wt %) results in the formation of compact PHB spherulites filling the whole space, whereas the noncrystallizable PPC spherical microdomains scatter in the PHB region, and their size shows a remarkable melting-time dependence. With the increasing PPC component and melting time, it is observed from POM that the separated PHB domains scattered in the continuous PPC phase, like the island structure. However, it can be revealed by SEM micrographs that the PHB thick domains are actually connected by its thin layer under the PPC layer. The real situation is, therefore, a large amount of PPC aggregates to the surface to form a network uplayer, whereas the PHB thick domains connected by its thin layer form a continuous PHB region, leading to a superimposed bilayer structure. There is also a small amount of PHB small domains scattered in the PHB phase. The PHB thick domains crystallize cooperatively with the PHB-or PHB-rich sublayer in a way just like the growth of pure PHB spherulites. This superimposed bilayer by interplay between phase separation and crystallization may provide availability to tailor the final structure and properties of crystalline/amorphous polymer blends.