Abstract: To address low selectivity, limited adsorption capacity, and poor cycling stability of flow-electrode materials in separating organic/inorganic anions, a carbonization-modified （or pyrolyzed） ZIF（Co/Zn）@PPy composite was fabricated by in situ growing bimetallic ZIF on a polypyrrole conductive network followed by pyrolysis at 900 ℃. Employed as a flow electrode in flow-electrode capacitive deionization （FCDI） for treating high-salinity wastewater containing cephalosporin antibiotics, the carbonized material exhibited a more developed mesoporous structure and superior electrochemical performance compared with the uncarbonized material, with markedly improved charge-transfer performance and an increase in charge efficiency from 74.06% to 95.50%. The NaCl adsorption capacity increased by 77%, and a separation factor of 13 635 was achieved with >97% capacity retention over 20 cycles. These findings highlighted the significantly enhanced performance, exceptional selectivity, and robust stability of the carbonized composite, demonstrating its potential for advanced electrochemical desalination, particularly for the selective separation of contaminants in high-salinity organic wastewater.