Thiamine is an essential micronutrient, but delivery of the vitamin in supplements or foods is challenging because it is unstable under heat, alkaline pH, and processing/storage conditions. Although distributed as a crystalline ingredient, thiamine chloride hydrochloride (TClHCl) likely exists in the amorphous state, specifically in supplements. Amorphous solids are generally less chemically stable than their crystalline counterparts, which is an unexplored area related to thiamine delivery. The objective of this study was to document thiamine degradation in the amorphous state. TClHCl:polymer dispersions were prepared by lyophilizing solutions containing TClHCl and amorphous polymers (pectin and PVP (poly[vinylpyrrolidone])). Samples were stored in controlled temperature (30–60 °C) and relative humidity (11%) environments for 8 weeks and monitored periodically by X-ray diffraction (to document physical state) and HPLC (to quantify degradation). Moisture sorption, glass transition temperature (Tg), intermolecular interactions, and pH were also determined. Thiamine was more labile in the amorphous state than the crystalline state and when present in lower proportions in amorphous polymer dispersions, despite increasing Tg values. Thiamine was more stable in pectin dispersions than PVP dispersions, attributed to differences in presence and extent of intermolecular interactions between TClHCl and pectin. The results of this study can be used to control thiamine degradation in food products and supplements to improve thiamine delivery and decrease rate of deficiency.