fields, such as integrated capacitors, energy harvesters, and hybrid electric vehicles. [1][2][3][4][5] In order to make good use of green energy, it is important to manufacture energy storage devices or equipment with high energy density. [6] Due to the requirement of energy storage technology, advanced batteries and capacitors with high energy density have been widely studied by scientists all over the world. Compared with other stored energy equipment, electrostatic capacitors are sole stored energy facilities that can charge quickly and provide the highest power density. [7][8][9][10][11] They are critical for many modern electronics and electrical applications. [1,12] At present, the demand for compact, reliable, and efficient power systems is increasing, and high-power capacitors are one of the main enabling technologies for the development of commercial, consumer, and military systems. [13][14][15] An important factor for quantifying dielectric material performance is the energy storage density (U e ), which is calculated as:where E, P, P max , and P r represent the applied electric field, the polarization, the maximum polarization, and the remnant polarization, [16] respectively. For linear dielectrics, the formula can be used:where ε 0 , ε r, and E b represent the vacuum constant, dielectric constant, and breakdown strength, respectively. Therefore, in order to obtain high U e , it is necessary to optimize E b and P max . [17][18][19][20] However, the most advanced commercial dielectric polymer biaxially oriented polypropylene (BOPP), due to its low dielectric constant, has a relatively low U e (≈3 J cm −3 ) even though it has a high E b . [21] Therefore, polymer composites have received great attention, and it is a common solving solution that inorganic materials with high dielectric properties and polymer matrix with high E b will be combined to obtain composites with excellent energy storage properties. [22][23][24][25] The high discharge energy density and excellent discharge efficiency are important indicators for measuring the performance of the capacitor. This work systematically studies the sandwich structure ceramic/polymer composites in which the original poly(vinylidene fluoride) (PVDF) is used as the outer layer, and the one-dimensional K 0.5 Na 0.5 NbO 3 nanofibers and PVDF composites are used as the intermediate layer. The experimental results show that the energy storage performance of the composite films can be effectively improved by rationally designing and optimizing the filler content. The finite element simulation verifies that the sandwich structure composites mainly reduce the electric field strength of the intermediate layer by adding ceramic fibers, which hinder the growth of the electric trees. In addition, reasonable filler content and optimized structural design can significantly reduce the electrical conductivity, thereby achieving excellent discharge efficiency. In the optimized sandwich structure composites, the high energy density of 14.2 J cm −3 and excellent discharge ef...