Single vitamin ingredients and blends in premixes are widely used in the food and supplement industries and are predominantly in powder form. To meet label claims and/or determine appropriate overages, it is important to characterize the stability of these ingredients. Although moisture is a known promoter of instability in powder blends, the combined effects of storage relative humidity (RH), formulation, and deliquescence on the stability of these systems are not well-characterized. The objective of this study was to determine the effect of deliquescence on the stability of vitamins B 1, B 6, and C and their mixtures. Deliquescence points (RH 0s) for all formulations were determined by moisture sorption analysis. Single, binary, ternary, and quaternary mixtures of thiamin HCl, pyridoxine HCl, sodium ascorbate, and fructose were stored in RH-controlled environmental chambers between 43 and 98% RH at 22 degrees C for up to 12 weeks. Vitamin stability was determined by high-performance liquid chromatography (HPLC). Formulation and storage RH significantly affected vitamin stability. Thiamin and ascorbate degradation were significantly promoted above the RH 0, while pyridoxine was least affected by storage RH. The deliquescence lowering phenomenon enhanced moisture sorption of blends at RHs below the RH 0s. Ascorbate enhanced thiamin degradation. Therefore, formulation, storage conditions, and the relation of these to deliquescence points may affect the shelf life, quality, and functionality of vitamin blends and should be considered in product development, processing, storage, and use.