Polyimides are important industrial materials because of their excellent properties. They are extensively used in the electronics industry and have great potential in the field of optical communications. In this article, we discuss the effect of the polyimide structure and the processing conditions on the optical properties. Both commercially available fluorinated polyimides and polyimides synthesized in our laboratory were used in this study. The relationship between the extent of fluorination and the refractive index was studied, and it was found that fluorination reduced the refractive index as expected. Studies conducted on the structure-property relationship revealed that with the use of more rigid monomers for the polyimides, the polyimides could be modified to show a large birefringence. The extent of birefringence depended on the composition of the polymer. In addition, the processing conditions directly controlled the residual stress in the polymer films. The residual stress was an important factor in inducing light scattering, which resulted in higher optical loss.