The high degree of complexation between metal ions and organic ligands presents a significant challenge to their removal via conventional chemical precipitation methods. Currently, oxidative decomplexation followed by alkali precipitation of Cu2+ represents an efficacious strategy for addressing Cu-ethylenediaminetetraacetic acid (Cu-EDTA). The efficacy of activated peracetic acid (PAA) processes in degrading contaminants has demonstrated excellent performance due to their higher oxidation potential. In this study, the UV/PAA process was initially employed for Cu-EDTA decomplexation, resulting in complete removal within 30 min. The 92.41 % released Cu2+ was successfully recovered by alkaline precipitation within 90 min. The mechanism of decomplexation is comprised of two principal stages. Firstly, the UV/PAA process gradually generates reactive oxygen species (ROS), including R-C•, •OH, and 1O2. These ROS facilitate the decomplexation of Cu-EDTA, resulting in the release of Cu2+. Additionally, Cu2+ can participate in the activated PAA, further promoting the production of ROS, which in turn enhances the removal of organic ligands. Furthermore, the transformation process of Cu-EDTA was subjected to analysis, along with the decomplexation products. Meanwhile, except for HCO3−, H2PO4−, and humic acid, which exerted a relatively minor impact on Cu2+ recovery, Cl− and NO3− demonstrated a negligible influence. Moreover, the reaction exhibits enhanced efficacy under acidic conditions and demonstrates robust performance in electroplating wastewater samples. In summary, this study provided a promising method for the decomplexation of Cu-EDTA efficiently and Cu recovery.