The water sorption of several starch samples and resistant starch (RS) samples were analyzed using an equilibrium solution-gel structure model and the results were compared to various sorption theories. It is found that the water sorption relations to water activity in starch in the high water content region could be properly described by the equilibrium two-phase structural model. The results suggested that favorable starch-starch interaction determined the formation of starch gel in water. The gel structure had a high molecular modulus of 10(8) Pa and thus had limited water sorption capability. Part of the starch also exhibited the solution properties with water due to chain ends and defects of the gel structure. Despite the unfavorable starch-water interaction, starch-water solution might be formed due to the predominant contributions from the entropy of mixing. The solution phase was responsible for the rapid increase of water sorption at high water activity. It was also demonstrated that the starch could maintain a maximum dynamic unfreezable water up to similar to 36%, which was consistent with the DSC measurements.