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% nanosized BaTiO3 (BT(nm)) particles was designed as a polymer–based matrix, which incorporates Ag–deposited micro–sized BaTiO3 (BT(μm)) hybrid particles. Interestingly, the dielectric permittivity at 103 Hz of the Ag–BT(μm)/PVDF–BT(nm) composites significantly increased from 114.0 to 165.2 with as the filler volume fraction increased from fAg–BT(μm) ≈ 0.4 to 0.5. Concurrently, the conductivity and loss tangent (tanδ < 0.09) were effectively suppressed compared to that of the PVDF–BT(nm) matrix (tanδ ≈ 0.31). The BT(nm) particles in Ag–BT(μm)/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(μm)/PVDF composite with fAg–BT(μm) ≈ 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(μm), Ag–BT(nm), and BT(nm)–BT(μm) interfaces), and hence the dielectric permittivity.