With the rapid development of modern electrical and electronic applications, the demand for high-performance film capacitors is becoming increasingly urgent. The energy density of a capacitor is dependent on permittivity and breakdown strength. However, the development of polymer-based composites with both high permittivity (εr) and breakdown strength (Eb) remains a huge challenge. In this work, a strategy of doping synergistic dual-fillers with complementary functionalities into polymer is demonstrated, by which high εr and Eb are obtained simultaneously. Small-sized titania nanosheets (STNSs) with high εr and high-insulating boron nitride sheets coated with polydopamine on the surface (BN@PDA) were introduced into poly(vinylidene fluoride) (PVDF) to prepare a ternary composite. Remarkably, a PVDF-based composite with 1 wt% BN@PDA and 0.5 wt% STNSs (1 wt% PVDF/BN@PDA−STNSs) shows an excellent energy storage performance, including a high εr of ~13.9 at 1 Hz, a superior Eb of ~440 kV/mm, and a high discharged energy density Ue of ~12.1 J/cm3. Moreover, the simulation results confirm that BN@PDA sheets improve breakdown strength and STNSs boost polarization, which is consistent with the experimental results. This contribution provides a new design paradigm for energy storage dielectrics.