In order to explore the effects of ceramics’ contents on composites’ macro-performance and microscopic structure, polyvinylidene fluoride/barium titanate composites were prepared by a coating technique. The PVDF/BaTiO3 (Bi4Ti3O12) composites are selected as research objects. It was observed that BaTiO3 (Bi4Ti3O12) powders with different ceramics’ contents affected the performance of PVDF/BaTiO3 (Bi4Ti3O12) composites’ dielectric. As the content of inorganic powders increases in some extent, dielectric constant of PVDF/inorganic powder composites increases. The microscopic structures of the materials were further studied. A red-shift was observed by Fourier transform infrared spectroscopy (FT-IR). Results of X-ray diffraction and FT-IR on PVDF/BaTiO3 showed that both the physical role (induction of β phase and interface defect) and the chemical bonding effect between BaTiO3 and PVDF affect the dielectric property of the composites. The chemical bonding effect was also observed in PVDF/Bi4Ti3O12 composites by FT-IR. Our results suggest that the intercoupling between fluorine in polyvinylidene fluoride and oxygen vacancy in barium titanates plays an important role in this kind of ferroelectric organic–inorganic composites. Overall, this paper provides some new and useful insights about the relationship between the physical property of PVDF/ceramic composites’ and composites’ microscopic structure.