Currently, there is an urgent demand for developing new materials to remove antibiotics in the water environment, especially for the simultaneous degradation of multiple antibiotics. Here, we fabricated a novel Bi/BiOBr heterostructure via an in situ solvothermal strategy, and it exhibited excellent visible-light-responsive photocatalytic activity for synchronously removing multiple antibiotics coexisting in water. The Bi nanoparticles could extend the light absorption spectra of the sample and further facilitate electron-hole pair separation. The in-depth electron spin resonance (ESR) results confirm that the active species in Bi/BiOBr are holes (h + ) and superoxide radicals (·O 2 - ) under irradiation, and it is also proved that Bi could selectively reduce the formation of ·O 2 - in the BiOBr matrix. The coexisting system of TC (tetracycline hydrochloride), CIP (ciprofloxacin) and DOX (doxycycline) could be simultaneously photodegraded to approximately 0% within 30 min by the Bi/BiOBr photocatalyst.