Defect engineering advantages include regulating the band structure of photocatalytic materials, inhibiting the recombination of photoelectron-hole pairs, and promoting the conversion of photogenerated electrons into active radicals. In this paper, bismuth molybdate (Bi2MoO6) photocatalysts with double vacancies (VBi-O-BMO) were prepared by solvothermal and ionic eutectic solvent methods. EPR, TEM, and XPS results confirmed the successful construction of oxygen and bismuth vacancies on Bi2MoO6. The photocatalytic performance of the prepared catalysts was investigated by photodegradation of levofloxacin hydrochloride (LVF) under visible light. The double vacancies markedly enhanced the photocatalytic properties of Bi2MoO6, with the photodegradation rate of VBi-O-BMO reaching 88.36 % for 40 mg/L LVF within 60 min. Kinetic studies have demonstrated that the reaction rate constant of VBi-O-BMO can reach 0.0351 min−1, which is 3.2 times higher than that of bulk-BMO. This can be attributed to the favorable synergistic effect of oxygen and bismuth double vacancies. VO not only captures oxygen and electrons, facilitating the generation of superoxide radicals (O2−), but also elevates the conduction band position and boosts the reduction capability of Bi2MoO6. VBi not only captures photogenerated holes (h+) to directly impact LVF degradation, but also promotes interfacial charge transfer and inhibits the recombination of electron-hole pairs. Furthermore, the intermediates and degradation pathways of LVF photodegradation were surmised based on the LC-MS analysis. The reaction mechanism of LVF photodegradation by VBi-O-BMO was elucidated through the application of the free radical pathway. This study demonstrates a methodology for the creation of double vacancies in catalysts and the significant potential of VBi-O-BMO for the remediation of antibiotic residues in water under visible light.