Optical probes based on polarized light spectroscopy, including spectroscopic ellipsometry (SE) and polarimetry, have been applied in research and process development for the three major thin-film photovoltaics technologies, including thin-film hydrogenated silicon (Si:H), cadmium telluride (CdTe), and copper indium-gallium diselenide (CuIn1−xGaxSe2). Real-time SE during materials fabrication has provided insights into the nucleation, coalescence, and structural evolution of these thin films. These insights have led, in turn, to guiding principles for PV performance optimization, as well as future directions for real-time process control. The optical properties deduced simultaneously with the layer thicknesses using real-time SE have been applied to characterize the phase composition of materials (amorphous versus crystalline), the mean free path and grain size, and the relative free carrier concentration. As a result, analytical formulae for the optical properties of PV materials have been developed with free parameters that are linked to basic materials properties. This paper shows how the formulae and associated parameter-property relationships can serve as a database for analyzing complete PV stacks, with future prospects for mapping layer thicknesses and basic materials properties in on-line monitoring applications for large-area PV plates and modules.