In this work two systems based on a carbohydrate polymer were studied: inulin as model system and inulin–orange juice as complex system. Both system were stored at different water activity conditions and subsequently characterized. Water adsorption isotherms type II were fitted by the GAB model and the water monolayer content was determined for each system. From thermal analyzes it was found that at low water activities (aw) systems were fully amorphous. As aw increased, crystallinity was developed. This behavior was corroborated by X-ray diffraction. In the inulin–orange juice system, crystallization appears at lower water activity caused by the intensification of the chemical interaction of the low molecular weight species contained in orange juice. Glass transition temperature (Tg), determined by modulated differential scanning calorimeter, decreased with aw. As water is adsorbed, the physical appearance of samples changed which could be observed by optical microscopy and effectively related with the microstructure found by scanning electron microscopy.