The moisture sorption behavior of developing cotton fibers is studied by dynamic vapor sorption. Mature fibers show a typical sigmoidal isotherm, IUPAC type II, describing the adsorption on macroporous and non-porous adsorbents with a typical hysteresis. This is different from the type III isotherms exhibited by elongating fibers explained by the weak adsorbate-adsorbent interactions. The maximum sorption capacity clearly decreases throughout the cotton fiber development. This decrease is very rapid during the elongation phase of the fibers, but declines beyond 25 days post anthesis (DPA). This transition corresponds to the time point where the secondary cell wall becomes dominant over the primary cell wall, as confirmed with FT-IR. Also only little moisture hysteresis appeared during the elongation phase whereas from 25 DPA onwards a distinct hysteresis is observed that remains almost constant until maturation of the fiber. The study clearly elucidates the sorption mechanism during the elongation phase of the fiber to be different from the one during the secondary cell wall synthesis. This improved understanding of the cotton sorption behavior is important for optimal application of cotton fiber in novel materials.