Miscibility, crystallization kinetics, crystal structure, and microstructure of biodegradable poly(butylene succinate-co-butylene adipate) (PBSA)/poly(vinyl phenol) (PVPh) blends were studied by differential scanning calorimetry, optical microscopy, wide angle X-ray diffraction, and small angle X-ray scattering in detail in this work. PBSA and PVPh are miscible as evidenced by the single composition dependent glass transition temperature and the negative polymer-polymer interaction parameter. Isothermal crystallization kinetics of PBSA/PVPh blends was investigated and analyzed by the Avrami equation. The overall crystallization rates of PBSA decrease with increasing crystallization temperature and the PVPh content in the PBSA/PVPh blends; however, the crystallization mechanism of PBSA does not change in the blends. Furthermore, blending with PVPh does not modify the crystal structure of PBSA. The microstructural parameters, including the long period, thickness of crystalline phase and thickness of amorphous phase, all become larger with increasing the PVPh content, indicating that PVPh mainly resides in the interlamellar region of PBSA spherulites in the blends. (C) 2009 Elsevier Ltd. All rights reserved.