Yu Zheng, Xiaohui Tang, Yanxi Qi, Shengbo Zhang, Na Ji
ABSTRACT Polyethylene terephthalate (PET), a major polyester, presents considerable environmental challenges due to its chemical stability and non‐biodegradability. Photo‐ and electrocatalysis offer promising sustainable approaches for PET valorization, benefiting from mild operating conditions and compatibility with renewable energy. This review systematically summarizes and elucidates the reaction mechanisms governing the photo‐ and electrocatalytic upgrading of PET‐derived ethylene glycol (EG) into high‐value chemicals by focusing on catalyst design strategies and structure‐activity‐selectivity relationships. Specifically, the directional coupling of EG with heteroatoms via C─X bonds (X = N, S) coupling reaction driven by photo‐/electrocatalysis is also highlighted. Combined with techno‐economic analysis (TEA) and lifecycle assessment (LCA), the industrial potential of these technologies is evaluated from economic and environmental sustainability perspectives. Finally, current challenges in the field are outlined, and future research directions are also proposed. This review provides insights for plastic resource utilization and the establishment of a circular economy, aiming to inspire innovation and advance the development of efficient catalysts and reaction systems integrated with plastic upcycling.