Nematic Ordered Cellulose (NOC) film that exhibits a noncrystalline yet highly ordered form was prepared by stretching a water-swollen cellulose gel obtained in a unique manner with coagulation of cellulose molecules dissolved in the N,N-dimethylacetamide/LiCl solvent system. In this article, structural characteristics of this unique film were investigated. Orientation of the molecular chains in the noncrystalline regions across the entire film were stable after immersing in water at room temperature, though conventional amorphous cellulose regions are in any forms believed fairly to be recrystallized under a humid atmosphere. Even 30 days after immersing in water at 50 degrees C, neither crystallization nor disordering of the chains occurred in the NOC film. On the contrary, the film was capable of being transformed into films composed of cellulose polymorphs domains where the molecular orientation was still maintained as the initial film under various mild conditions that both cotton and cellophane did not show any changes on their structure. These contradictory properties of the NOC film proved to be dependent on its unique supermolecular structure. (c) 2007 Wiley Periodicals, lnc.