The trisaccharide raffinose was prepared in its crystal pentahydrate, anhydrous methanolate, and amorphous forms and evaluated with regard to dehydration and hydration properties at various temperatures and relative humidities. The pentahydrate, when stored at relative humidities (RHs) of < 60% but > 10%, showed no loss of water after 3 months of storage at 30 degrees C. When stored below 10% RH, only one water molecule could be removed over a period of 3 months, whereas within 24 h at 30 degrees C in a vacuum oven, two water molecules were removed with no change in crystal structure. Increasing the temperature to 60 degrees C progressively removed the remaining three molecules, causing the crystal, however, to collapse into an amorphous form identical to one prepared by lyophilization. Rehydration at 30 degrees C, which was sufficient to reduce the glass transition temperature to < 30 degrees C, rapidly restored the pentahydrate crystal structure. Rehydration of the methanolate also restored the pentahydrate structure. The significant amount of water accommodated by raffinose in both the crystalline and amorphous forms would appear to make it a potentially useful water scavenger in certain types of dosage forms.