Changes of the molecular dynamics of water in 5% corn starch pastes and 5% systems composed of starch and non-starchy hydrocolloid were studied during short and long term retrogradation. Low Field NMR was used to record mean correlation times (τc) of water molecules. This molecular parameter reflects the rotation of water molecules within the network of paste. Starches of different amylose and amylopectin content were selected for this study. Comparison of the changes of τc shows how particular polymers bind water molecules. During 90 days of storage, over 50% increase in mean correlation time was recorded in pastes of starches with high amylose content. This suggests that the formation of polymeric network is controlled by amylose to which water is binding. Amylopectin was found to influence the mobility of water in the pastes to a lesser extent with changes in mean correlation times of approximately 10–15% over 90 days. On retrogradation, amylopectin, Arabic and xanthan gums hindered the formation of solid phase structures. Guar gum evoked an increase in mean correlation times of approximately 40–50% during the prolonged process of changes of the molecular dynamics of water. This indicates continued expansion of the polymeric network. Mean correlation time available from spin–lattice and spin–spin relaxation times can be useful in the analysis of the rotational vibrations of the water molecules in biopolymeric structures.