Energy storage film is one of the most important energy storage materials, while the performance of commercial energy storage films currently cannot meet the growing industrial requirements. Hence, this work presents a h-BN/PVDF/h-BN sandwich composite structure film prepared by laminating a large area of ultrathin hexagonal boron nitride (h-BN) and polyvinylidene fluoride (PVDF), the existence of which was confirmed by using an optical microscope and elemental composition analysis based on scanning electron microscopy and X-ray diffraction. This film has an ultrahigh dielectric strength of 464.7 kV/mm and a discharged energy density of up to 19.256 J/cm3, which is much larger than the commercial energy storage film biaxially oriented polypropylene (BOPP) (