High-performance films with almost zero-birefringence and zero-wavelength dispersion were succeeded to prepare from pullulan esters derivatives (PLEs) without any additives. Optical transmittance analysis, birefringence measurement of PLE cast film and hot stretched films, and infrared dichroism analysis were conducted to characterize optical properties of PLE films comparing with cellulose triacetate which is commercially used as low-birefringence in optical devices. The aims of this study, characterization of optical properties of pullulan esters, can develop a deep understanding of the fundamental knowing and applicability of polysaccharides. Accordingly, authors believe this paper will open the gate for researches in the application of polysaccharides.