A study on blends of thermoplastic polyurethane elastomer (TPU)/poly(vinylidene fluoride) (PVDF) is described. This investigation focused on the effects that PVDF has on the mechanical behaviors and morphological characteristics of the blends. Basic thermodynamic and structural considerations were applied to predict the blend miscibility. It was found that addition of PVDF disrupted the intermolecular chain interactions in TPU, resulting in lowering of mechanical properties in the blends. Our results showed that the 50/50 blend has the lowest mechanical strength. At higher levels of PVDF (>50%), the mechanical strength increased proportionally to PVDF. It was also found that both the breaking strain and the energy at break of these blends decreased with increased PVDF content. The lowering of the mechanical properties in the blends could be attributed to the formation of layered structures caused by the immiscibility of the polymers. It was concluded that TPU/PVDF blends were incompatible at all compositions.