The chain conformation of an arabinoxylan isolated from the rice endosperm cell wall, which was composed of the linear backbone of a 1,4-linked beta-xylose residue highly substituted at the C3 position with alpha-L-arabinofuranose, was studied by X-ray fiber diffraction and a conformational analysis. From the X-ray results the polysaccharide was suggested to take an extended left-handed, three-fold helical structure which is not a desirable conformation to make a complex firmly associated with cellulose or xyloglucan that was elucidated to be present in the cell wall. A conformational analysis, using the PFOS force field for the O-alpha-L-arabinofuranose-(1-->3)-beta-D-xylose residue and O-alpha-L-arabinofuranose-(1-->3)-[(1-->4)-beta-D-xylose residue]3, in which the arabinose residue was linked to the C3 position of the middle residue of the xylotriose residue, and using the PS79 computer program for the arabinoxylan indicated that the backbone xylan chain could not take a two-fold helix similar to that of cellulose because of significant steric interaction between the arabinose side chain and the backbone. Thus, the left-handed, three-fold helix was found to be reasonable.