The dilute nanocomposite strategy facilitates a promising route for high-temperature polymer dielectrics to achieve high dielectric constant and energy density, robust breakdown strength, and low loss. The dielectric enhancement of the dilute nanocomposites strongly ties to the topological conditions of the nanofiller–polymer interface. Here, atomic force microscopy-based infrared spectroscopy was employed to observe the interfacial region of a high-temperature poly(arylene ether urea) (PEEU) dilute nanocomposite directly. The experimental results showed that the nanoparticles induce morphological changes in PEEU, and the interface region extends over 150 nm away from the nanofiller surfaces. Such nano-morphology changes are highly indicative of generating a large enhancement of the dielectric performance in the PEEU dilute nanocomposite.