Some natural fibers like flax, hemp and others show excellent mechanical properties that make them a promising choice for the reinforcement of polymers. The increasing research on natural fiber reinforced composites has still left important questions open, mainly concerning the fiber-matrix interface. Compared to the well optimized glass fibers, cellulose fibers show very different interaction with matrix polymers and adhesion promoters. The hydrophilic cellulose structure allows for the penetration of a considerable amount of water into the amorphous regions of the fibers, eventually exceeding 20% by mass, depending on fiber type, preparation and environmental humidity. Even embedded in totally apolar polymers the cellulose partly retains its ability for water sorption, which results in unfavorable effects, such as dimensional changes, decrease in strength, roughening of the surface, etc. The interaction of differently prepared fibers with water vapor and the effect of surface treatment is investigated by measuring the dynamics of water vapor sorption. An exponential model is used for the numerical evaluation of the sorption and desorption kinetics. The model not only allows for an excellent fit of the experimental isotherms, but without any further assumptions it immediately gives evidence of the existence of two distinct mechanisms for the exchange of water vapor, related to different sorption sites. These specific mechanisms are represented by individual sorption-desorption isotherms as components of the total isotherms. The model provides a clearer differentiation of the effects of fiber preparation and modification with respect to interfacial interactions.