Native cellulose consists of a set of parallel chains composed of glucose. Most of the time, these chains are highly ordered and form a structure that is known as a microfibril. On the other hand, highly crystalline forms of cellulose are more difficult to process and often are unpredictable in their behavior. If an ordered but noncrystalline form of cellulose could be produced, this would greatly extend the possibilities of usage of cellulose to new areas. In this paper, we have produced such a new supermolecular structure of cellulose, called nematic ordered cellulose. The unique characteristics of this supermolecular structure of cellulose have been clarified using various kinds of physicochemical analyses. Using a high-resolution transmission electron microscopic approach, we have also imaged the single glucan chains, demonstrating the close but nonprecise association usually found in crystalline biopolymers.