Crystallization and the polymorphic transition of poly(vinylidene fluoride) (PVDF) in its miscible blends with poly(butylene succinate) (PBS) from the melt has been investigated. The presence of a miscible PBS component lowers the crystallization temperature and the melting point of the PVDF component in the blends. It becomes more significant above a critical PBS content between 40 and 50 wt % where PVDF chains are dispersed in the matrix composed by PBS chains. On the other hand, the β form of the PVDF component can be induced at low temperatures, which also has a transition at the critical PBS content.