This paper describes the processing of silver-nanoparticle-doped poly(vinylidene fluoride). The effects of the concentration and size of the filler on the electroactive phase of the polymer and the optical and electrical properties are discussed. Spherical silver nanoparticles incorporated into the poly(vinylidene fluoride) polymeric matrix induce nucleation of the electroactive γ phase. The electroactive phase content strongly depends on the content and size of the nanoparticles. In particular, there is a critical nanoparticle size, below which the filler losses its nucleation efficiency due to its small size relative to that of the polymer macromolecules. Furthermore, the presence of surface plasmon resonance absorption in the composites is observed, which once again shows a strong dependence on the concentration and size of the particles. The absorption is larger for higher concentrations, and for a given concentration increases with particle size. This behavior is correlated to the electrical response and is related to the extra bands and electrons provided by the nanoparticles in the large energy band gap of the polymer.