The synthesis of a new cross-linked structure, with sucrose and diepoxide monomers, possessing the properties of a highly swellable hydrogel polymer is reported. Characterization studies of its structure and water effects were carried out in dried and hydrated samples by CP-MAS C-13 n.m.r., by wide-band H-1 and H-2 n.m.r. and by differential thermal analysis. The results indicate that the sample is completely amorphous and disordered, that methyl groups are present and that there is strong water structuring due to hydrogen bonding, with an absence of free water at low levels of hydration. Two processes are manifest in the temperature dependence of the 2H line width.