Polypropylene film is the most important organic dielectric in capacitor technology; however, applications such as power electronic devices require more miniaturized capacitors and thinner dielectric films. The commercial biaxially oriented polypropylene film is losing the advantage of its high breakdown strength as it becomes thinner. This work carefully studies the breakdown strength of the film between 1 and 5 microns. The breakdown strength drops rapidly and hardly ensures that the capacitor reaches a volumetric energy density of 2 J/cm3. Differential scanning calorimetry, X-ray, and SEM analyses showed that this phenomenon has nothing to do with the crystallographic orientation and crystallinity of the film but is closely related to the non-uniform fibers and many voids produced by overstretching the film. Measures must be taken to avoid their premature breakdown due to high local electric fields. An improvement below 5 microns will maintain a high energy density and the important application of polypropylene films in capacitors. Without destroying the physical properties of commercial films, this work employs the ALD oxide coating scheme to augment the dielectric strength of a BOPP in the thickness range below 5 μm, especially its high temperature performance. Therefore, the problem of the reduction in dielectric strength and energy density caused by BOPP thinning can be alleviated.