To deliver their functionality when used in applications, citrus fibers need to be rehydrated. Factors such as chemical composition, structural organization as well as chemical surface composition are known to influence this functionality. Processing and storage conditions can affect these parameters, making it challenging to maintain stable functionality. This study used Fourier-transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) to evaluate the effects of preparation and storage on citrus fibers. Samples dried at different scales and stored for 360 days under room and accelerated conditions were assessed for water holding capacity (WHC), water swelling capacity (WSC), and gel rigidity (G′). The results showed a decline in WHC, WSC, and G′ over time, confirming that aging negatively impacts moisture retention, particularly under higher water content or temperature. Drying scale had no effect on chemical composition or structure, but changes in the elemental surface composition of carbon and oxygen were noted. While prolonged storage altered the polysaccharides' chemical composition and structure, leading to functionality loss, XPS analysis revealed no changes in surface composition. Loss of functionality cannot be explained by chemical surface composition modifications.