Combining electrocatalytic oxygen reduction reaction (ORR) and heterogeneous electro-Fenton (HEF) reaction is considered a promising approach for generating reactive radicals to decompose organic micropollutants in water.A novel catalyst, copper-cobalt carbon aerogel (CuCo/CA), was successfully fabricated and directly applied as a bifunctional cathode in an HEF system.The synergistic effect of Cu and Co contributed to the development of distinctive microstructures, including abundant oxygen-containing groups, carbon defects, a large surface area and a unique porous structure.These structural features endowed CuCo/CA with rapid electron transfer capability and enhanced activity and selectivity for the two-electron ORR process.In the constructed EF system, CuCo/CA achieved its dual functionality by catalyzing the electrosynthesis of hydrogen peroxide and its in situ activation to generate highly reactive hydroxyl radicals.Notably, anodic oxygen evolution in the system eliminated the need for addnl. oxygen input, enhancing its cost-effectiveness.The system demonstrated degradation ability for a range of candidate organic pollutants, including antibiotics, analgesics, organic acid and dye.After six consecutive runs, CuCo/CA EF system achieved satisfactory TC removal and good adaptability within a broad pH range.Long-term stability and low electricity consumption highlighted the potential of CuCo/CA as an efficient and sustainable cathode in EF technol. for water decontamination.