In the research study, the effect was analysed of gelatinization temperature on water binding in native and waxy potato starch pastes using a low-field NMR field. The study was conducted at a molecular level in the pastes at concentrations between 0.01 and 0.05 g/g. An empirical distribution model was suggested of correlation times that determined the molecular dynamics of free and bound water fractions in pastes. That model broadens knowledge about the polymer-polymer and polymer-solvent interactions in starch systems. Compared to the native potato starch, the waxy potato starch was characterized by a clear lead of polymer-polymer interactions over the polymer-water interactions. Based on the results obtained, it was concluded that the water molecules had an advantageous affinity to the starch in the native starch pastes prepared at 95 °C. The pastes of waxy potato starch pasted at 121 °C bound the least water.