Small-deformation dynamic oscillation and differential scanning calorimetry were used to ascertain the role of water molecules in high sugar/polysaccharide glasses. Increasing replacement of water with sugar affects adversely tahe degree of order in the polysaccharide network to such an extent that at level of solids >90% structure formation is no longer possible. Depending of the polymeric ability to form a network, the rheological T(g) can be up to 30 degrees higher than the calorimetric T(g).