The interactions of cellulose with other major plant cell wall polysaccharides - arabinoxylan (AX), xyloglucan (XG) and mixed linkage glucans (MLG) - have been investigated by characterising the architecture of composite deuterated cellulose hydrogels by means of SAXS and SANS, combined with XRD, NMR and microscopy. The results indicate that cellulose-AX interactions, limited to the ribbons' surface, take place via a non-specific adsorption mechanism. In contrast, XG and MLG interact specifically with cellulose, forming two different fractions: (i) interfibrillar domains interacting with the cellulose microfibrils and (ii) surface domains, responsible for the cross-linking of ribbons. XG co-crystallises with cellulose, promoting the formation of Ib-richer microfibrils and forming intercalated amorphous regions. On the other hand, MLG interacts with cellulose forming a paracrystalline coating layer. This structural role of XG and MLG in preventing microfibril aggregation may help explain their key function in the cell expansion process of growing plant tissues. (C) 2017 Elsevier Ltd. All rights reserved.