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Cationization of cotton is considered to be an effective way to realize salt-free dyeing of reactive dyes. However, applying cotton modified with glycidyltrimethylammonium chloride (GTA) suffers from large consumption of the cationic reagent. One of the reasons is that high crystallinity of cotton fibers hinders the penetration of the reagents into the cellulose interior and limits the reaction between them. This paper designed to use alcohol-water-NaOH system to pretreat the fibers before cationization. With this method, crystallinity of the cotton fibers is decreased and more reactive –OH is exposed, resulting in much higher fiber-reagent reactivity and increased GTA utilization. Influence of alcohol type, alcohol-to-water ratio, and quantity of NaOH on fiber crystallinity and GTA dosage for cationization are all examined. It is found that for achieving 96.0% fixation of C.I. Reactive Black 5 in the absence of salt, GTA dosage can be reduced by half when the fibers are pretreated by alcohol-water-NaOH. Compared with ethanol, n-propanol and isopropanol, tert-butyl alcohol incorporated system shows better performance in increasing fiber reactivity due to their weaker ability to dissolve ions. In this study, XRD and FT-IR are used to demonstrate changes in crystallinity of the fibers after pretreatment. The alteration in micromorphology and hydrophilicity of the pretreated fibers is observed by SEM and water contact angle test, respectively. Furthermore, the alcohol-water-NaOH system can be recycled to show very good repeatability. Notably, all dyed samples pretreated with the system present high color saturation and satisfactory color fastness, especially that the wet rub fastness reaches 4–5 grade, which is one grade higher than that obtained from the conventional dyeing with salt. The above findings prove that alcohol-water-NaOH pretreatment is effective in enhancing reactivity of the cotton fibers and penetrability of the agent, and it shows promising prospects in real application. Full article