We report a method to improve the dielectric constant (ε′) of polyvinylidene fluoride (PVDF) composites by using a low content of Ag nanomaterials deposited reduced Graphene Oxide (rGO) Hybrid Particles (Ag-rGO HPs). The Ag-rGO HPs are prepared by a reaction between silver nitrate and ethylene glycol in a seed-mediated growing process. The dispersion of Ag nanomaterials was completely homogeneous on the surface of rGO nanosheets with particle sizes of 5.765 ± 0.189 nm. The Ag-rGO HPs/PVDF composites were produced by a liquid–phase assisted dispersion and hot-pressing methods. The high ε′ at 103 Hz for Ag-rGO/PVDF composites with fAg-rGO 7.8, and 11.9 vol% was 153 and 683, respectively. The best-fitting curve was completely achieved in percolation theory by adjusting fc = 14 vol%. The high ε′ (683 at 1 kHz) of Ag-rGO/PVDF could be explained by Maxwell Wagnare Sillars interfacial polarization and micro-capacitor due to the formation of a sandwich between Ag-rGO and PVDF.