Hydrothermal oxidation, a promising method for removal of cobalt radionuclides from EDTA-containing liquid radioactive waste streams, is in the focus of the present study. It has been demonstrated that Co(III)-EDTA complexes, which are very stable under normal conditions, undergo oxidation as a result of the electron transfer from the EDTA carboxyl group to Co(III) ions under elevated temperature. The electron transfer reaction follows the first-order rate law with an activation energy of 91.8 kJ/mol at pH 12 and time of Coale ions half-conversion of 0.2 s at 200 degrees C. The rate of EDTA oxidation is proportional to the concentration of Co(III) ions and solution pH. Based on quantum chemistry simulations, possible intermediate structures formed upon the electron transfer from EDTA to Co(III) ions have been suggested. It has been shown that the introduction of hydrogen peroxide provides a continuous generation of Co(III) ions and a sequential decarboxylation of the EDTA until complete degradation of the chelate structure. The pathways of cobalt immobilization have been clarified.