Ferroelectric BaTiO3/polyvinylidene fluoride (BaTiO3/PVDF) composites were prepared by a coating technique. It was observed that BaTiO3 powders prepared with different thermal treatment temperatures affected dielectric performances of the composites. The polymer with fine BaTiO3 powder exhibited a lower dielectric loss than that with coarse powder. Fourier transform infrared spectrum was carried out to investigate the vibration of chemical bonds. The relationship between the dielectric property and intercoupling between F- ion and oxygen octahedron was discussed.