ABSTRACT Polyethylene terephthalate (PET), one of the most popular plastics, leads to serious environmental challenges due to its massive consumption and limited recyclability. Traditional recycling methods suffer from low efficiency and poor product value. Recently, electrocatalytic upcycling has emerged as a promising strategy to convert PET wastes into value‐added chemicals under mild conditions. This review first introduces an electrocatalytic approach, including alkaline hydrolysis of PET to ethylene glycol (EG), followed by the anodic oxidation of EG. This subsequent EG oxidation reaction (EGOR) enables the selective C1 and C2 products such as formate and glycolate, while simultaneously generating hydrogen at the cathode. We discuss the latest advances in catalyst design on Ni‐based non‐precious nanomaterials and supported ones, as well as the mechanistic understanding based on experimental and theoretical studies. Moreover, the review highlights the synergistic role of catalyst composition, surface structure, and reaction conditions in steering the selectivity and efficiency during the EGOR process. In addition, challenges and future directions on the hydrolysis process of PET, engineering of robust catalysts, EGOR mechanism, and potential industrial implementation are highlighted. Overall, the dual benefits of chemical valorization and green hydrogen production positions this electrochemical strategy as a sustainable and economically attractive solution for PET plastic recycling.