The specular and off-specular X-ray reflectivities were efficiently employed to study the evolution of surface morphology as a function of temperature in a single layer of poly（3-hydroxybutyrate） （PHB） and a bilayer of PHB/poly（vinyl phenol） （PVPh） on Si substrates. The results indicate that the changes of thickness and surface roughness caused by pre-melting of PHB crystals are not obvious for the single layer, whereas the surface roughness of the PHB layer and the intensity of the off-specular X-ray reflectivity for the bilayer exhibit a remarkable non-monotonic change in the temperature range of 100-150℃; the roughness parameter evaluated by the specular X-ray reflectivity reaches its maximum at 120℃. The interaction at the interface between PVPh and PHB certainly contributes to the non-monotonic changes. Such interaction also affects the crystallization and melting behavior of PHB thin film greatly. The crystallization of PHB thin film is inhibited even on the glassy surface of PVPh sublayer, In the melting process, the PHB crystals on PVPh sublayer feature a threesection melting curve separated by a plateau region of 120-140℃.
