The ubiquity of nonbiodegradable polyethylene terephthalate (PET) materials has led to significant waste management challenges. Although PET plastics can be recycled, blended materials, such as PET/cotton fabrics, complicate the recycling process due to the labile glycosidic bonds in cotton. In this study, we present a practical and scalable approach for recycling of PET and PET/cotton interwoven fabrics via catalytic glycolysis with ammonium bicarbonate (NH₄HCO₃), which decomposed to ammonia, carbon dioxide, and water. This catalytic approach outperformed conventional acid/base and metal catalysis in selectively recovering and upcycling cotton-based materials. We demonstrated the large-scale recovery of textile from blended fabrics (up to 213 g), showcasing the advantages of traceless catalysis using ammonia and CO₂ from ammonium bicarbonate. Owing to our metal-free reaction conditions, high-purity bis(hydroxyethyl)terephthalate (BHET) was obtained which was thermally repolymerized to PET. Through thermal analysis, kinetics, and control experiments, we show that ammonia and CO₂ are crucial for achieving optimal glycolysis via transesterification. Our method offered a traceless, environmentally friendly, and practical approach for polyester recycling and cotton recovery, representing a significant step toward sustainable, closed-loop production of plastics and textiles.