This paper describes the processing of silver nanoparticle doped poly(vinylidene fluoride). The effect of the dopant concentration on the α- to β-phase transformation of the polymer as well as in the morphological, thermal, optical and dielectric properties of the nanocomposites was investigated. Spherical silver nanoparticles were incorporated into the poly(vinylidene fluoride) polymeric matrix by the solvent casting method, with different Ag concentrations. Well-dispersed Ag nanoparticles act as nucleation centers, increasing the degree of crystallinity of the nanocomposites. Homogeneous dispersion of silver nanoparticles is demonstrated through the presence of surface plasmon resonance absorption in the nanocomposites. The α- to β-phase transformation was achieved in the polymer matrix and a maximum of ≅70% of β-PVDF was reached at 80 °C and a stretching ratio of 400%. The dielectric constant of the nanocomposites increases with increasing metal nanoparticle concentration, up to ≅26 at 0.020 wt% Ag content. The α- to β-phase transformation affects both the dielectric response and the surface plasmon resonance.