We demonstrate the synthesis of a novel core-satellite-structured BaTiO-poly(dopamine)-silver (BT-PDA-Ag) nanoparticle for improving dielectric properties of nitrile-butadiene rubber (NBR) nanocomposites. The BT-PDA-Ag nanoparticles are synthesized by dopamine oxidative polymerization and electroless plating of silver. The Ag nanoparticles decorated on the BT nanoparticles enhanced the dielectric constant of NBR nanocomposites due to the increased conductivity of the filler/matrix interlayer and nanocapacitor structure. In addition, the incorporation of the BT nanoparticles prevented the continuous connection of Ag nanoparticles and suppressed the formation of a conductive path in the NBR matrix. Moreover, the ultrasmall Ag nanoparticles trapped the carriers by Coulomb blockade and quantum confinement effects, which results in low dielectric loss and electrical conductivity of nanocomposites. The proposed method with simplicity and scalability can be adapted to process high-dielectric polymer nanocomposites.