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Summary: Of prime importance in reactions involving insoluble cellulosic fibers is the sorption of reagents, which is governed by their degrees of accessibility in substrates. Swelling treatments of cellulosics in alkali solutions alter substrate accessibility leading to changes in their reactivity. In this paper, the first of a two-part series, we collate and examine the results from various studies involving different techniques to characterize modifications in cellulosic fibers after swelling treatments in alkali solutions. Results from measurements of structure and accessibility in fibers with techniques such as water retention, inverse size exclusion chromatography (ISEC), iodine sorption, fiber diameters, and fiber-splitting propensities indicate that the influence of swelling treatments on fiber structure/accessibility is differs with alkali type. The results show that a non-uniform rather than uniform distribution of reagents within structures is a more accurate representation of reactions involving swollen cellulosic fibers. Hence, the observed changes in cellulose-fiber reactivity are governed by the degrees of fiber swelling, and reagent sorption and accessibility during swelling treatments.