The effect of metal-semiconductor Zn-ZnO core-shell structure on dielectric properties of polyvinylidene fluoride (PVDF) composites was investigated. Zn-ZnO fillers were obtained by the heat-treatment of raw Zn particles under air. The enhanced dielectric constant of Zn-ZnO/PVDF composites results from the duplex interfacial polarizations induced by metal-semiconductor interface and semiconductor-insulator interface. The dielectric loss is still low because of the presence of ZnO semiconductor shell between Zn metal core and insulator PVDF matrix. Furthermore, the dielectric performance of as-prepared composites could be further optimized through adjusting the thickness of semiconductor shell.