Bean cells that have been habituated to grow in a lethal concentration (12 μM) of 2,6-dichlorobenzonitrile(dichlobenil or DCB, a cellulose biosynthesis inhibitor) are known to have decreased cellulose content in their cell walls.Xyloglucan, which is bound to cellulose and together with it forms the main loading network of plant cell walls, has also been described to decrease in habituated cells, but whether the change on cellulose affects the xyloglucan structure besides its abundance has not been analyzed. Fragmentation analysis with xyloglucan-specific endoglucanase (XEG) and endocellulase revealed that habituation to DCB caused a change in the fine structure of xyloglucan, namely a decrease in fucosyl residues attached to the galactosyl-xylosyl residues along the glucan backbone. After the removal of herbicide from the medium (dehabituated cells), xyloglucan recovered its fucosyl residues. In addition, some cello-oligosaccharides could be detected only in habituated cells’ xyloglucan digested by XEG and endocellulase, corresponding to a glucan covalently bound or co-precipitated with the hemicelluloses. These results show that structural flexibility of cell walls relies in part on the plasticity of xyloglucan composition and opens up new perspectives to further research in this field.