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Among homogeneous catalysts, cobalt ions exhibit ultra-high persulfate activation performance. In this work, an electrically supported medium Co(II) activated peroxydisulfate synergistic process was established to eliminate organic contaminants in water. The synergistic catalytic effect was verified by comparing the oxidative degradation performance and reaction rate constant of different coupling systems. The decolorization ability of E-Co(II)-PDS on reactive black 5 (RB5) was explored, and the results showed that the removal rate of RB5 can reach 93.21% under the optimized conditions of current density of 5.71 mA/cm2, initial pH of 4, Co(II) concentration of 0.2 mM and PDS concentration of 5 mM. The effect of water matrix on the removal of RB5 was studied, and it was found that HCO 3 − and humic acid significantly inhibited the degradation of RB5, while Cl− and H 2 PO 4 − could effectively promote it at a certain concentration. Notably, the degradation of RB5 in E-Co(II)-PDS system achieved lower energy consumption, with an energy consumption per unit volume (EE/O) value of 0.4304 kWh·m−3. EPR test, quenching experiments and contribution rate analysis showed that the oxidation active species in E-Co(II)-PDS process were Co(III), sulfate radicals and hydroxyl radicals, and their oxidation contribution rates were 15.72%, 12.69% and 53.25%, respectively. Finally, the decomposition process of RB5 was proposed by the mass spectrometry results. The electric current promotes cobalt ion cycling and PDS activation through electron transfer, and induces Co(II) to promote the activation of PDS, which is the main mechanism of E-Co(II)-PDS system to achieve the robust degradation ability of RB5. • Co(II) greatly improved the activation effect of electroactivated persulfate system. • The current promotes Co(II)/Co(III) cycling and peroxydisulfate activation. • Low energy consumption was achieved by E-Co(II)-PDS system. • Co(III), SO 4.•– and •OH contributed to RB5 removal in E-Co(II)-PDS process. • E-Co(II)-PDS could robustly degrade organic contaminants in water. [ABSTRACT FROM AUTHOR]