Characterization of thin film solid oxide fuel-cell materials can be difficult due to the range of porosities in electrodes and electrolytes as well as the nano-sized pores and particles. In this study, optical characterization techniques such as ultraviolet–visible transmission and reflection spectrophotometry are illustrated as methods for achieving information about the film density from the film refractive index as well as the film thickness. These techniques were used to investigate the sintering process of colloidal CeO2 on sapphire substrates and polymeric precursor-derived ZrO2:16%Y (YSZ) thin films on silicon over the temperature range 400–1000 °C, and the results were compared with traditional characterization techniques such as electron microscopy, profilometry, ellipsometry, and x-ray diffraction line broadening analyses. Most of the techniques were in good agreement with the CeO2 grain size changing from 5–65 nm and the film thickness changing from 0.8–0.5 μm. Comparisons of transmission and reflection spectrophotometry with ellipsometry illustrated that scattering effects from the porous CeO2 films caused an overestimation of the refractive index from ellipsometry, but allowed for accurate grain size measurements from transmission and reflection data. Both techniques were in good agreement during the sintering of the YSZ thin films, with the density changing from 90–100% theoretical after heating between 400 and 800 °C.