AbstractThe NMR relaxation times T1 and T2 for starch polysaccharides in solution were employed for the characterization of bound and free water. The “Solomon equations” were taken for the calculation of the amount of bound water in maltodextrin‐water systems. The amount of monomolecular bound water in maltodextrin solutions and gels is independent on the state in the same order of magnitude as estimated for maltodextrin powders from water vapour sorption isotherms. With increasing temperature between 1°C and 60°C a slight decrease of bound water was found.