Carbendazim (CBZ), as a highly effective benzimidazole fungicide, has a good control effect on various crops caused by fungi. However, excessive use of CBZ in water, atmosphere, soil, and crops has serious effects. The efficient degradation of CBZ is an effective way to reduce its toxic effect. In this work, the type of Sscheme Ag/AgBr/BiOBr heterojunction photocatalyst was effectively prepared by a simple one-step solvothermal in situ method and first applied to the mineralization and degradation of CBZ. The effects of the molar ratio of AgBr to BiOBr, catalyst dosage, CBZ concentration, pH value of the original solution, and inorganic salt ions on the photocatalytic degradation performance of CBZ were comprehensively studied. The results showed that, under visible light irradiation, 0.9-Ag/AgBr/BiOBr (0.9-AAB) exhibited the best photocatalytic degradation performance (88.9%) against the concentration at 10 mg/L of CBZ in original solutions with pH of 10. However, the degradation effect was also good at pH 7. After 90 min, the degradation efficiency reached 86.0%, corresponding to a TOC removal efficiency of 84.0%. The results indicate that the main active species are 1 O 2 and • O 2 − free radicals according to the free radical quenching experiments and electron spin resonance spectra. Combined with the XPS characterization results, the electron transfer mechanism of the S-scheme heterojunction was deeply revealed. Additionally, the degradation pathway of CBZ was proposed through both the intermediate identification and the theoretical calculation derived from the DFT Fukui index. Finally, the toxicity of CBZ and the degradation intermediates were predicted based on the T.E.S.T.