The absence of long-wavelength shoulders in the spectra, which are associated with oscillations of non-spherical particles or plasmon coupling of aggregates, has confirmed SEM data on high uniformity of the Ag/chitosan composite films. We have shown that the refractive index of the composites at a wavelength of a HeNe laser (633 nm) increases from 1.53 to 1.69 with the increase of the silver volume fraction up to 2.55%. Investigations of composites waveguiding properties revealed that the light propagation is feasible up to a silver volume fraction of 1.3%, which corresponds to the maximum refractive index 1.58