Starch is a natural plant raw material applicable in many areas of industry. In practice, it is most often used in a modified form, i.e., after various treatments aimed at modifying its properties. Modifications of native starch enable producing resistant starch, which, as a prebiotic with confirmed health-promoting properties, has been increasingly used as a food additive. The present study aimed to determine the effect of roasting retrograded starch with the addition of anhydrous glucose at different temperatures (110, 130 or 150 °C) and different times (5 or 24 h) on the modified starch’s properties. The results of high-performance size-exclusion chromatography coupled with refractive index detector (HPSEC/RI) analysis and the changes observed in the solubility of starch roasted with glucose in DMSO, as well as in its other properties, confirm the changes in its molecular structure, including thermolytic degradation and the ongoing polymerization of starch with added glucose.