The influence of the poly(N-ethyl-2-ethynylpyridinium iodide) (PEEP-I) concentration on the morphology and optical properties of nanocomposite systems prepared by mixing the polymer solution with a hydrosol of ca. 9 nm Ag nanoparticles (NPs) was investigated by a combination of surface plasmon extinction (SPE) measurements, transmission electron microscope (TEM) imaging and surface-Raman spectroscopy (SERS).