Polymer nanocomposites with the dielectric constant comparable to that of percolative composites are successfully prepared by using core-shell structured hyperbranched aromatic polyamide grafted barium titanate (BT-HBP) hybrid nanofiller. Poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene) (PVDF-TrFE-CFE) was used as the polymer matrix because of its high intrinsic dielectric constant and easy processability. The BT-HBP hybrid nanofiller were prepared by a solution polymerization of diaminobenzoic acid on the surface of amino-funcationalized BT nanoparticles. Nuclear magnetic resonance ((1)H NMR) and transmission electron microscopy (TEM) were used to verify the chemical structure of the hyperbranched aromatic polyamide and core-shell structure of the hybrid filler, respectively. It was found that the nanocomposite with 40 vol % BaTiO3-HBP had a dielectric constant of 1485.5 at 1000 Hz, whereas the corresponding nanocomposite sample with untreated BaTiO3 only showed a dielectric constant of 206.3. Compared with classic percolative composites, the advantage of the PVDF-TrFE-CFE/BaTiO3-HBP nanocomposites is that the composites show high enough breakdown strength and high dielectric constant simultaneously. An enhanced interfacial polarization mechanism between the BT-HBP and the polymer matrix was suggested for understanding the observed unusually high dielectric constant.