The objective of this study was to address the challenges posed by the short retention time and inadequate targeting of thiamine in vivo. To this end， a rice starch-thiamine delivery system (DM-VB) was engineered through a hydrothermal method， whereby the opening and polymerization of the starch molecular structure were regulated. The impact of temperature， time， starch concentration， and thiamine addition on the structural stability， thiamine loading capacity， and release characteristics of the delivery system was thoroughly investigated. The structural integrity of the system was examined through scanning electron microscopy and X-ray diffraction. The findings revealed that the primary interaction mode between starch and thiamin was through hydrogen bonding， with a subset of thiamin molecules accessing the helical cavity of starch. The loading amount of thiamin exhibited a substantial influence on the release characteristics， with higher loading amounts correlating to higher contents of slow-digested starch. The results demonstrated that the constructed starch-thiamin delivery system exhibits excellent stability and slowed release， which suggested significant potential for application in the domain of functional foods. This finding not only unveiled a novel approach for the delivery of water-soluble small molecules but also provided a comprehensive understanding of the preparation method and release control mechanism of starch-based functional foods. This knowledge was of paramount importance for the advancement of functional food development.