Bi₂O₃/F–TiO₂ composites were successfully synthesized via an aqueous precipitation method. Their morphologies, structures and photocatalytic performance in the degradation of methyl orange (MO) were characterized by scanning electron microscopy, X-ray diffraction, UV-vis absorption spectroscopy and photoluminescence spectroscopy. The results show that the Bi₂O₃/F–TiO₂ composites exhibit enhanced photocatalytic performance in the degradation of MO with a maximum degradation rate of 95% under visible light irradiation for 180 min, which is mainly ascribed to the increase in light adsorption and the reduction in electron–hole pair recombination in Bi₂O₃ with the introduction of F–TiO₂.