Two optical systems are used for characterizing free-standing highly birefringent polymer films. The first system is the Michelson interferometer and is utilized, in the presence of a polarizer, to determine the refractive indices in the two principal vibration directions along and across the axis of the sample, and the birefringence. The second system directly determines the birefringence. It is based on measurements of the optical path difference and the light intensity before and after striking the sample. The results show that the obtained values of birefringence, by the two methods, are in good agreement with each other. Certain optical parameters related to the measured values of refractive indices and birefringence are also calculated. The used methods are recommended for investigating thick and highly birefringent materials, where the conventional methods face certain problems such as the large number of interference fringe order and the highly refractive indices of the used immersion liquids.