Overall crystallization behavior and polymorphism of partially miscible poly(vinylidene fluoride) (PVDF)/poly(ethylene oxide) (PEO) blends were systematically investigated over the whole composition range. Isothermal and non-isothermal experiments were carried out using a differential scanning calorimeter (DSC). Since the components of the blend crystallize separately due to substantial difference in their melting points, the changes in melting, crystallization and equilibrium melting temperatures of PVDF and PEO as well as their degree of crystallization were evaluated. Solid-liquid phase transition (SLPS) temperatures of the PVDF/PEO blends were measured and the results verified the previously determined miscibility window. As the binary blends display LCST-type phase diagram, the crystallization behavior and kinetics are strongly affected by the miscibility state of the blends in the melt state. For the blends with high content of PEO, the occurrence of phase separation and presence of the pre-existing PVDF crystals result in higher degree of crystallization in PEO component. Wide-angle X-ray diffraction (WAXD) and Fourier transform infrared spectroscopy (FTIR) were also utilized to investigate the crystallization polymorphism of PVDF and PEO in as-prepared blends.