Traditional processes usually cannot enable efficient water decontamination from toxic heavy metals complexed with organic ligands. Herein, we first reported the removal of Cu(II)-EDTA by a UV/chlorine process, where the Cu(II)-EDTA degradation obeyed autocatalytic two-stage kinetics, and Cu(II) was simultaneously removed as CuO precipitate. The scavenging experiments and EPR analysis indicated that Cl• accounted for the Cu(II)-EDTA degradation at diffusion-controlled rate (∼1010 M-1 s-1). Mechanism study with mass spectrometry evidence of 11 key intermediates revealed that the Cu(II)-EDTA degradation by UV/chlorine was an autocatalytic successive decarboxylation process mediated by the Cu(II)/Cu(I) redox cycle. Under UV irradiation, Cu(I) was generated during the photolysis of the Cl•-attacked complexed Cu(II) via ligand-to-metal charge transfer (LMCT). Both free and organic ligand-complexed Cu(I) could form binary/ternary complexes with ClO-, which were oxidized back to Cu(II) via metal-to-ligand charge transfer (MLCT) with simultaneous production of Cl•, resulting in the autocatalytic effect on Cu(II)-EDTA removal. Effects of chlorine dosage and pH were examined, and the technological practicability was validated with authentic electroplating wastewater and other Cu(II)-organic complexes. This study shed light on a new mechanism of decomplexation by Cl• and broadened the applicability of the promising UV/chlorine process in water treatment.