Fenton method combined with light to accelerate the production of free radicals from H
2O
2 can achieve more efficient pollutant degradation. In this paper, a novel BiOI/FeWO
4 S-scheme heterojunction photocatalyst was obtained by in situ synthesis, which can activate H
2O
2 and degrade the organic pollutant OFC (ofloxacin) under visible light. The S-scheme charge transfer mechanism was confirmed by XPS spectroscopy, in situ KPFM and theoretical calculation. The photogenerated electrons were transferred from FeWO
4 to BiOI driven by the built-in electric field and band bending, which inhibited carrier recombination and facilitated the activation of H
2O
2.The BiFe-5/Vis/H
2O
2 system degraded OFC up to 96.4% in 60 min. This study provides new systematic insights into the activation of H
2O
2 by S-scheme heterojunctions, which is of great significance for the treatment of antibiotic wastewater.