Molecular modeling is used to investigate the ways in which plant cell wall xyloglucans might bind to the surface of cellulose microfibrils. Binding involving the xyloglucan backbone is found to be sterically restricted. Plausible models are obtained that involve hydrogen bonding between the xylose residues and one kind of cellulose surface. In such a model, the xyloglucan sidechains mediate, as well as modulate, the binding.