Abstract: The persulfate activation technology, as one of the advanced oxidation technologies, can significantly improve the performance of materials degradating pollutants when coupled with photocatalysis. ZnO@N, C-Co₃O₄ was fabricated from ZIF-67/8 through hydrothermal method. The optical absorption range of ZnO was expanded to the visible light region and the recombination of photogenerated carriers was effectively inhibited. The chemical composition, morphology and light absorption properties of the composite film electrode were characterized, and the photoelectrochemical properties were degradation studied. The highest rate of degrading Tetrabromobisphenol A(TBBPA) from the thin film electrode in the persulfate-enhanced photocatalytic system was 97.2%, which indicated that the coupling of the persulfate activation technology and photocatalysis significantly enhanced the efficiency of catalytic degradation of TBBPA from ZnO@N, C-Co₃O₄. The mechanism of photoelectrocatalytic degradation of TBBPA assisted with persulfate was studied. Sulphate radical and hydroxyl radical were the main active species in the system.