Currently, society expects convenience food, which is healthy, safe, and easy to prepare and eat in all conditions. On account of the increasing popularity of modified potato starch in food industry and its increasing scope of use, this study focused on improving the physical modification of native starch with temperature changes. As a result, it was found that the suggested method of starch modification with the use of microwave power of 150 W/h had an impact on the change in starch granules. The LF-NMR method determined the whole range of temperatures in which the creation of a starch polymer network occurs. Therefore, the applied LF-NMR technique is a highly promising, noninvasive physical method, which allows obtaining a better-quality structure of potato starch gels.