AbstractFlexible dielectrics with large dielectric constant (ε′) coupled with low loss are highly pursued in many applications. To bolster the ε′ of raw Zn (zinc)/poly(vinylidene fluoride, PVDF) while maintaining pimping dielectric loss, in this study, the core@double–shell structured Zn@zinc carbonate (ZnCH)@polystyrene (PS) particles are first synthesized through a suspension polymerization of styrene, and then composited with PVDF to elevate the ε′ and keep low loss of the composites. By optimizing the PS shells’ thickness and tailoring the electrical resistivity of Zn@ZnCH@PS particles, both the slow inter‐particle polarization and fast intra‐particle polarization in the composites can be decoupled and synergistically tuned, thus, the Zn@ZnCH@PS/PVDF achieves a much higher ε′ and lower dielectric loss, simultaneously, which far exceed the unmodified Zn/PVDF. Both experiment and theoretic calculation reveal that the double‐shell ZnCH@PS not only induces and promotes multiple polarizations enhancing the composites’ ε′, especially at the optimized PS's thickness, but also maintains suppressed loss and conductivity thanks to their obvious barrier effect on long‐range charge migration. The core@double–shell filler design strategy facilitates the development of polymer composites with desirable dielectric properties for applications in electronic and electrical power systems.