In this study, we employed three kinds of Zn particles, i.e., raw flaky Zn (f-Zn), spherical Zn (s-Zn) with self-passivation layer of ZnCH, and core–shell structured ZnO@Zn (c-Zn). Therefore, the present research is expected to provide a deeper insight into the effects of the shape and core–shell structure of Zn particles on the dielectric properties and thermal conductivity of the PVDF