Ultrathin multilayers are important for electrical and optical devices, as well as for immunoassays, artificial organs, and for controlling surface properties. The construction of ultrathin multilayer films by electrostatic layer-by-layer deposition proved to be a popular and successful method to create films with a range of electrical, optical, and biological properties. Dendrimer nanocomposites (DNCs) form highly uniform hybrid (inorganic-organic) nanoparticles with controlled composition and architecture. In this work, the fabrication, characterization, and optical properties of ultrathin dendrimer/poly(styrene sulfonate) (PSS) and silver-DNC/PSS nanocomposite multilayers using layer-by-layer (LbL) electrostatic assembly techniques are described. UV-vis spectra of the multilayers were found to be a combination of electronic transitions of the surface plasmon peaks, and the regular frequency modulations attributable to the multilayered film structure. The modulations appeared as the consequence of the highly regular and non-intermixed multilayer growth as a function of the resulting structure. A simple model to explain the experimental data is presented. Use of DNCs in multilayers results in abrupt, flat, and uniform interfaces.