The photovoltaic properties of CdTe-based thin films depend on recombination levels formed in the CdTe layer and at the heterojunction. The localized states are resultant of structural defects (metal sublattice, chalcogen sublattice, interstitial), controlled doping, deposition process, and/or post-deposition annealing. The photoluminescence study of CdTe thin films, from both the bulk and heterojunction, can reveal radiative states due to different defects or impurities. Identification of defects allows for potential explanation of their roles and influence on solar cell performance. A thorough understanding of the material properties responsible for solar cell performance is critical in further advancing the efficiency of devices. The presented work is a systematic investigation using photoluminescence to study CdTe thin films with varying deposition processes. The thin (polycrystalline) films explored in this study were deposited by either the elemental vapor transport technique (EVT) or close spaced sublimation (CSS). Two device architectures were investigated, the typical CdTe/CdS device and the CdSeXTe1-X (CST) alloy device. Post-deposition annealing processes were either laser or thermal. The study of the CdTe thin films is grouped in three general categories: (a) EVT films: Intrinsic and Extrinsic (Group V: Sb and P), (b) CST alloys, and (c) Post-deposition Laser Annealed (LA) films. The main goal of this dissertation is to understand the influence of fabrication procedures (deposition conditions, post deposition thermal and chemical treatments, added impurities, and device architecture) on the defect structure of the CdTe thin films. The behavior of the photoluminescence (PL), studied as a function of the measurement temperature and excitation intensity, provides insight to the mechanism causing the radiative recombination levels. Analysis of the PL spectra for CdTe films with intrinsic doping demonstrated stoichiometric control of native defects for both the Cd- and Te-rich conditions. PL spectra of CdTe:Sb films showed unique Sb-related bands. Also, impurity-related defects were identified in the CdTe:P spectra. Spectral analysis support the need for optimization of dopant concentration. The effects of selenium (Se) thickness and post-deposition processing on the formation of CST alloy were demonstrated in the changing PL spectra. The native defects (and complexes) identified in films with thermal anneal processing were the same as those identified in films with laser anneal post-deposition processing. The PL data were collected and other characterization techniques were used to support the defect assignments. A repository of material properties, which include the recombination levels along with structural defect assignment for each of the CdTe deposition processes, is provided. This project will lend the solar cell community information on CdTe defects for different processing conditions, ultimately influencing the fabrication of improved solar cells.