Chalcogenide glasses and their use in a wide range of optical, electronic and memory applications, has created a need for a more thorough understanding of material property variation as a function of composition and in geometries representative of actual devices. This study evaluates compositional dependencies and photo-induced structural mechanisms in As-S-Se chalcogenide glasses. An effective fabrication method for the reproducible processing of bulk chalcogenide materials has been demonstrated and an array of tools developed, for the systematic characterization of the resulting material's physical and optical properties. The influence of compositional variation on the physical properties of 13 glasses within the As-S-Se system has been established. Key structural and optical differences have been observed and quantified between bulk glasses and their corresponding as-deposited films. The importance of annealing and aging of the film material and the impact on photosentivity and long term behavior important to subsequent device stability have been evaluated. Photo-induced structures have been created in the thin films using bandgap cw and sub-bandgap femtosecond laser sources and the exposure conditions and their influence on the post-exposure material properties, have been found to have different limitations and driving mechanisms. These mechanisms largely depend on both structural and/or electronic defects, whether initially present in the chalcogenide material or created upon exposure. These defect processes, largely studied previously in individual binary material systems, have now been shown to be consistently present, but varying in extent, across the ternary glass compositions and exposure conditions examined. We thus establish the varying photo-response of these defects as being the major reason for the optical variations observed. Nonlinear optical material properties, as related to the multiphoton processes used in our exposure studies, have been modeled and a tentative explanation for their variation in the context of composition and method of evaluation is presented.