The novel concept of combining Ag-deposited BaTiO3/poly(vinylidene fluoride) (PVDF) is proposed using a three-phase composite system employing various sizes of BaTiO3. A mixture of 80 vol% PVDF-20 vol% nano-sized BaTiO3 (BT(nm)) particles was designed as a polymer-based matrix, which incorporates Ag-deposited micro-sized BaTiO3 (BT(mu m)) hybrid particles. Interestingly, the dielectric permittivity at 10(3) Hz of the Ag-BT(mu m)/PVDF-BT(nm) composites significantly increased from 114.0 to 165.2 with as the filler volume fraction increased from f(Ag-BT(mu m)) approximate to 0.4 to 0.5. Concurrently, the conductivity and loss tangent (tan delta < 0.09) were effectively suppressed compared to that of the PVDF-BT(nm) matrix (tan delta approximate to 0.31). The BT(nm) particles in Ag-BT(mu m)/PVDF-BT(nm) composites partially inhibited the formation of conduction pathways in the PVDF polymer, retaining low values of the conductivity and loss tangent. Without BT(nm) particles, the dielectric permittivity of the Ag-BT(mu m)/PVDF composite with f(Ag-BT(mu m) )approximate to 0.4 was only 68.6. Thus, the BT(nm) particles gave rise to shorter interparticle distances between the filler particles and increased the total interfacial areas (i.e., Ag-PVDF, Ag-BT(mu m), Ag-BT(nm), and BT(nm)-BT(mu m) interfaces), and hence the dielectric permittivity.