The morphological features and mechanical properties of PVDF/PBS blends with a variety of blend ratios and under different preparation conditions have been studied by optical and atomic force microscopy, as well as by tensile tests. It was found that, at high PVDF crystallization temperature, a small amount of PBS in the 70/30 PVDF/PBS blends has been expelled into the PVDF spherulite margin areas and interspherulitic regions due to the high diffusion ability of PBS and the slower crystal growth rate of the PVDF at high temperature. Nevertheless, the PBS affects the crystallization of PVDF significantly, which has been revealed by the increase in birefringence of PVDF spherulites of both α and γ types and the increase in band period of the α PVDF spherulites. With increasing PBS content, the increase in birefringence of PVDF spherulites and the increase in band period of the α PVDF spherulites get more evident, reflecting a more efficient influence of PBS on the crystallization of PVDF. In the PBS-rich blends, e.g., in the 40/60 and 30/70 PVDF/PBS blends, the PVDF forms isolated spherulites with large non-crystallizing PBS melt regions, which results in an interspherulitic phase separation with bigger interspherulitic PVDF areas. There is, however, PBS dispersed within the PVDF spherulites. During the crystallization of PBS at low temperature, it was found that the PBS in the interspherulitic and interaspherulitic regions growth in different manner with different growth rates. At lower PVDF crystallization temperatures, the PVDF crystallizes first and fills all the volume in regardless its content in the blends. This leads to the PBS being distributed in the interlamellar or interfibrillar regions of PVDF spherulites only. However, the growth of PBS in banded and non-banded PVDF matrix is different, reflecting the influence of pre-existing PVDF crystals on the crystallization of PBS. Tensile test shows that the deformation behavior depends remarkably on the blend ratio and the crystallization temperature of the PVDF. Such phenomena has been correlated and explained in view of the inner morphological change.