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We examined birefringence in a stretched film of cellulose triacetate (CTA) after extraction of an immiscible component. The CTA film plasticized by di(2-ethylhexyl) adipate (DOA), which was added as the immiscible additive, exhibited negative birefringence to the same degree as the pure CTA film. Following removal of DOA from the film by immersion into methanol, the birefringence of the blend film changed dramatically from negative to positive. Moreover, the wavelength dependence also changed from ordinary to extraordinary, in which the absolute value of birefringence increases with wavelength. Scanning electron microscope (SEM) images revealed nanoscale ellipsoidal pores in the film after the extraction, suggesting that DOA was segregated and formed ellipsoidal domains in the CTA matrix during annealing and stretching. According to an optical theory for the nanoporous structure, we found that the form birefringence contributes to control of the optical properties of the CTA film. This phenomenon could be utilized in the design of high-performance optical films, such as quarter waveplate, because sign and wavelength dispersion of birefringence can be controlled even for a single component film.