<p>Polymer nanocomposite dielectrics hold immense potential as film capacitor materials in the upsurge of electrical energy storage. The interface in polymer nanocomposite dielectrics is suggested to play decisive roles on the bulk material performance. However, the limitations of bulk polymer-based composites using the nanoscale hybrid approach, especially in co-dispersed systems, lie on the coupling interaction of multiple matrix/particle interfaces imposed by phase separation and nanofiller agglomeration. This positions polymer nanocomposites as usually required to a trade-off between dipole activity, breakdown resistance, and heat tolerance. Here, we present a laminated polymer nanocomposite film where the polyetherimide component is hierarchically combined with carbon-based conductors and wide-bandgap inorganics, understanding the underlying mechanisms of phase distribution, interface decoupling, and interlayer recombination between the polymer matrix and foreign nanofillers. Our findings demonstrated that the nanofiller incorporation and multilayer fabrication enable nanocomposite films to attain a balance of capacitive performance, including enhanced polarization, suitable breakdown, and stable thermal characteristics. Such a configurational design is dedicated to a combination of features and properties from various dielectric layers, highlighting how hierarchically laminated structures possess a viable, accurate, and flexible edge on tailored modulation of capacitive performance.</p>