The main objective of this thesis is to investigate the layer-by-layer deposited polyelectrolyte and polyelectrolyte/metal nanoparticle films by using X-ray Photoelectron (XPS) and Optical Spectroscopy (UV-Vis). Within this purpose, in the first part of the study, layer-by-layer deposited single and oppositely charged bilayered films are investigated by XPS. To extract additional information in the molecular level, the samples are analyzed while applying an external voltage bias. It is shown that applying external electrical stimuli to a single polyelectrolyte layer coated Si/SiO2 system responds to the change in the polarity by molecular rearrangements, evidenced by the changes only in the intensity of the corresponding –N + (1s) peak. In the second part of the study, metal nanoparticle (Au and/or Ag) incorporated polyelectrolyte films are investigated by optical spectroscopy. Within this frame, multilayer gold and silver nanaoparticle/polyelectrolyte films are prepared both separately and in bimetallic form. In order to get further understanding about the optical responses of single type of metal nanoparticle incorporated systems, several experimental approaches are followed. These approaches also enable us to control and manipulate the optical properties of these compact structures. The last part focuses on incorporation of metallic ions into layer-by-layer assembled polyelectrolyte matrices through ion-exchange method. It is shown that metal ions can be incorporated and subsequently reduced within this polymer matrix by UV or X-ray irradiation and can also form nanoparticles.