Electron spin resonance (ESR) was used in order to study interaction of starch polysaccharides (amylose and amylopectin), their mixture and gelatinized potato starch with water molecules and lipids upon cooling. Different spin probes were used, on the one hand spin-labelled stearic acid (5-DSA), which limited lipids, and on the other hand the water soluble probe 4-hydroxy-2,2,6,6 tetramethylpiperidine-loxyl (Tempol), which was sensitive to changes in dynamic water phase associated with the temperatureinduced polysaccharide gel formation. It was shown that interaction between gelatinized starches and lipids related to mainly on presence of amylose macromolecules in the system. On the other hand, interaction between amylopectin macromolecules and lipids takes place also.