Ceramic-polymer composites have attracted extensive attention in electrical applications due to their high permittivity and low loss. In this work, we report the studies on the preparation and properties of barium titanate (BT)/ poly(vinylidenefluoride) (PVDF) composite thin films. The composite film was prepared by a modified process rather than the conventional method. The modified process adopted ballmilling technique instead of the stirring method to disperse BT nanoparticles into PVDF solution. Scanning electron microscopy images of the obtained composites show that the BT nanoparticles are incorporated into the PVDF network and are well dispersed in the matrix. When the BT volume fraction is 30%, the permittivity and breakdown strength of the composites reach their optimal values and the energy density reaches maximum value (5.3 J/cm3), an increase of 80% compared with that of the composites prepared using the stirring method. Another modification is the use of acetone and butanone mixed solution instead of N,N-dimethylformamide to dissolve the PVDF, which is beneficial to form pure α-PVDF composite films on the polyethylene terephthalate substrate by tape casting. The composites prepared by the modified process, with high permittivity and significantly enhanced breakdown strength, are useful candidates for energy storage applications.