Dielectric materials with high electric energy densities and low dielectric losses are of critical importance in a number of applications in modern electronic and electrical power systems. An organic–inorganic 0–3 nanocomposite, in which nanoparticles (0-dimensional) are embedded in a 3-dimensionally connected polymer matrix, has the potential to combine the high breakdown strength and low dielectric loss of the polymer with the high dielectric constant of the ceramic fillers, representing a promising approach to realize high energy densities. However, one significant drawback of the composites explored up to now is that the increased dielectric constant of the composites is at the expense of the breakdown strength, limiting the energy density and dielectric reliability. In this study, by expanding the traditional 0–3 nanocomposite approach to a multilayered structure which combines the complementary properties of the constituent layers, one can realize both greater dielectric displacement and a higher breakdown field than that of the polymer matrix. In a typical 3-layer structure, for example, a central nanocomposite layer of higher breakdown strength is introduced to substantially improve the overall breakdown strength of the multilayer-structured composite film, and the outer composite layers filled with large amount of high dielectric constant nanofillers can then be polarized up to higher electric fields, hence enhancing the electric displacement. As a result, the topological-structure modulated nanocomposites, with an optimally tailored nanomorphology and composite structure, yield a discharged energy density of 10 J/cm3 with a dielectric breakdown strength of 450 kV mm–1, much higher than those reported from all earlier studies of nanocomposites.