In recent years, water pollution caused by organic pollutants and antibiotic residues has become increasingly serious, posing a serious threat to human health and ecosystems. In this paper, Co–BiVO4/Bi2O3 heterojunction was successfully prepared by electrospinning of Co3+ doped monoclinic BiVO4 nanofibers and Bi2O3. The photocatalytic degradation of chlortetracycline hydrochloride (CTC·HCl) and 2-mercaptobenzothiazole (MBT) in water was tested by simulating visible light conditions. The degradation efficiency of CTC·HCl by 3Co–BiVO4/Bi2O3-0.8 reached 90.5 % within 30 min, and the degradation rates were 3.93 and 7.06 times that of BiVO4 and Bi2O3, respectively. At the same time, the degradation efficiency of MBT by 3Co–BiVO4/Bi2O3-0.8 reached 97.7 % within 40 min, and the degradation rates were 8.93 and 41.80 times that of BiVO4 and Bi2O3, respectively. In addition, the photocatalytic performance of the catalyst and potassium persulfate (PS) co-system on pollutants was investigated. When 0.5 mM PS and a small amount of 3Co–BiVO4/Bi2O3-0.8 catalyst were added, the degradation efficiency of CTC·HCl and MBT could reach 87.6 % and 92.8 % in a short time. Furthermore, the work function and difference of the material were calculated by density functional theory (DFT), and the charge transfer mechanism of the p-n heterojunction was further determined. Finally, the intermediate products, degradation pathways and reaction mechanisms of MBT degradation were analyzed in detail by high performance liquid chromatography-mass spectrometry (HPLC-MS). Therefore, this study provides a potential effective way for the treatment of water pollution.