Chalcogenide glasses are being investigated for waveguide and integrated optical component applications. In order to advance the novel properties exhibited by these glasses, it is crucial to identify the structure/property relationship in both bulk and film materials. Rutherford backscattering spectroscopy was used to obtain compositional, structural, and thickness information on the chalcogenide film structures. Results obtained showed no apparent variation in composition and small density variation in single layer As2S3 films. Multilayer films, in which thicknesses were measured using scanning electron microscope images, displayed compositional and density modifications associated with the annealing process. After a 1 year aging interval, the same analysis was conducted to ascertain changes induced by film aging. Stoichiometric and thickness modifications, caused by aging, were observed in nonannealed structures. No apparent changes were detected in annealed films. Raman spectroscopy was used as a complementary tool to identify the molecular features responsible for these changes.