Dielectric polymer nanocomposites with high dielectric constant have wide applications in high energy density electronic devices. The introduction of high dielectric constant ceramic nanoparticles into a polymer represents an important route to fabricate nanocomposites with high dielectric constant. However, the nanocomposites prepared by this method generally suffer from relatively low breakdown strength and high dielectric loss, which limit the further increase of energy density and energy efficiency of the nanocomposites. In this contribution, by using core-satellite structured ultra-small silver (Ag) decorated barium titanate (BT) nanoassemblies, we successfully fabricated high dielectric constant polymer nanocomposites with enhanced breakdown strength and lower dielectric loss in comparison with conventional polymer-ceramic particulate nanocomposites. The discharged energy density and energy efficiency are derived from the dielectric displacement-electric field loops of the polymer nanocomposites. It is found that, by using the core-satellite structured Ag@BT nanoassemblies as fillers, the polymer nanocomposites can not only have higher discharged energy density but also have high energy efficiency. The mechanism behind the improved electrical properties was attributed to the Coulomb blockade effect and the quantum confinement effect of the introduced ultra-small Ag nanoparticles. This study could serve as an inspiration to enhance the energy storage densities of dielectric polymer nanocomposites.