Chemical recycling of textiles holds the potential to yield materials of equal quality and value as products from virgin feedstock. Selective depolymerization of textile polyester (PET) from regenerated cellulose/PET blends, by means of alkaline hydrolysis, renders the monomers of PET while cellulose remains in fiber form. Here, we present the mechanism and reactivity of textile PET during alkaline hydrolysis. Part I of this article series focuses on the cellulose part and a possible industrialization of such a process. The kinetics and reaction mechanism for alkaline hydrolysis of polyester packaging materials or virgin bulk polyester are well described in the scientific literature; however, information on depolymerization of PET from textiles is sparse. We find that the reaction rate of hydrolysis is not affected by disintegrating the fabric to increase its surface area. We ascribe this to the yarn structure, where texturing and a low density assures a high accessibility even without disintegration. The reaction, similar to bulk polyester, is shown to be surface specific and proceeds via endwise peeling. Finally, we show that the reaction product terephthalic acid is pure and obtained in high yields. © 2022 by the authors.