The photoluminescence properties of nanocomposite materials based on polyvinylidene fluoride (PVDF) with a filler of ZnS are studied in the wavelength region of λ = 300–1000 nm. PVDF powder with a particle size of 0.5–1.0 μm is used as the matrix. It is shown that an increase in the concentration of the initial solutions leads to an increase in the size of the ZnS nanoparticles in the PVDF; that is, in the process of the cluster formation, the coalescence of the ZnS particles into a nucleation center takes place. It is also found that the composites exhibit a shift of their luminescence bands to shorter wavelengths at a decrease in the concentration of nanoparticles in the matrix and, consequently, in the size. This can be explained by both the reabsorption of the luminescence in the optically dense scattering sample and a change in its spectral composition.