The problem of low charge/discharge efficiency of ceramic/polymer composites is still one of the hot topics in current research on dielectric materials. Here, we demonstrate that the ferroelectric property of ceramic/PVDF-based composites can be modulated by the introduction of linear polymer PI and the use of a spin-coating process. PI inhibits some polarization and partial dipole orientation by interacting with the molecular chains of the amorphous phase of PVDF and BT nanoparticles. As a result, the decrease in crystallinity and loss led to improved dielectric properties and charge/discharge efficiency. The findings demonstrate that the microstructure of PVDF-PI/BT nanocomposite is uniform and dense, with outstanding dielectric characteristics and high charge/discharge efficiency. The permittivities were stabilized in the range of 12.87–17.86 at 100 Hz, and the dielectric losses were all less than 0.27. Compared with the previously reported binary ceramic/polymer composites, the PVDF-PI/BT nanocomposites possessed a high charge/discharge efficiency with a small variation (63%-84%). This work offers an easy and efficient scheme to obtain nanocomposites with outstanding dielectric characteristics and charge/discharge efficiency. It may be a potential candidate for flexible dielectric substrates for advanced flexible capacitive energy storage devices.