High dielectric (high-k) polymer nanocomposites that can electrostatically store energy are widely used in electronics and electric power systems due to their high breakdown strengths (E b ), durability, and ability to configure in various shapes. However, these nanocomposites suffer from a limited working temperature regime, thus limiting their extreme applications, such as hybrid and electric vehicles, aerospace power electronics, and deep ground fuel exploration. Furthermore, the E b and the electric displacement (D) of polymer nanocomposites must be simultaneously enhanced for high-density capacitor applications, which prove to be difficult to modify concurrently. This chapter thoroughly reviews (investigates) the recent developments in the high-k polymer nanocomposites synthesis, characterization, and energy storage applications. Consequently, the aim of this chapter is to provide an overview of the novel developmental strategies in order to develop high-dielectric nanocomposites perovskite ceramics that can be incorporated in high-energy-density (HED) applications.