Classical chemical precipitation technology is inefficient for the removal of heavy metal-organic complexes from wastewater. In this study, a novel and green strategy of coupling bicarbonate-activated hydrogen peroxide (BHP) oxidation and alkaline precipitation was proposed for simultaneous decomplexation of Cu-ethylenediaminete-traacetic acid (Cu-EDTA) and Cu precipitation. The Cu-EDTA decomplexation efficiency reached 92.0% within 60 min of the BHP treatment, and the decomplexation process was spontaneous and endothermic. Reactive substances such as center dot O-2(-), center dot OH, and O-1(2) were identified, and center dot O-2(-) was predominant in the Cu-EDTA decomplexation. The weak alkaline environment provided by bicarbonate favored the generation of the reactive substances and subsequent Cu-EDTA decomplexation. Relatively higher H2O2 dosage favored Cu-EDTA decomplexation, while excessive bicarbonate dosage inhibited the reaction. TOC removal efficiency and Cu removal efficiency reached 78.4% and 68.3% after 60 min treatment, respectively. The Cu-O and Cu-N bonds in Cu-EDTA were destroyed by the reactive substances, and a series of Cu-containing intermediates, small organic molecules such as ethanamine, ethylene glycol and butanediol, and NO3- were produced. The released Cu ions were precipitated as Cu-2(OH)(2)CO3, CuCO3, Cu(OH)(2), and CuO. Possible pathways of Cu-EDTA decomplexation in this system were proposed.