The combination of H-1 magic angle spinning (MAS) n.m.r. and two-dimensional nuclear Overhauser enhancement spectroscopy (NOESY) is shown to be readily applicable to hydrogels. This is demonstrated in the superabsorbing polymer, hydrolysed starch-g-poly(acrylonitrile), which readily responds to hydration. Enhanced molecular mobility of the polymer is directly revealed by polymer-polymer NOESY connectivities. The two-dimensional experiment also reveals the presence of an efficient cross-relaxation mechanism between the water of hydration and the polymer.