Polyethylene terephthalate (PET) is widely used, yet the accumulation of its waste poses serious environmental challenges, making efficient recycling essential. PET glycolysis using EG as solvent has emerged as a green‑recycling strategy. In this study, cyclic alkylamino carbene copper (CAAC‑Cu) complex was prepared as catalyst for PET glycolysis. Under optimized conditions (160 °C, 90 min, catalyst amount 3 wt %, and PET:EG=1:4.), PET conversion reached 98.2 %, the selectivity toward BHET was 88.1 %, and the yield was 86.5 %. Kinetic analysis indicated that the glycolysis follows first‑order kinetics with an activation energy of 98.7 kJ mol⁻¹. In addition, the catalyst can be recovered together with excess EG, and after multiple recycles, PET degradation remained above 95 % and BHET yield stayed above 80 %. A possible mechanism has also been proposed, Cu acts as a Lewis acid coordinating to the carbonyl oxygen of PET, facilitating ester bond activation, while the amino‑carbene forms hydrogen bonds with EG, assisting bond cleavage in a Brønsted‑base manner. This catalytic system provides a novel and efficient approach for the green, high‑performance glycolysis of PET.