Abstract: The selective oxidation of cyclohexane to cyclohexanol and cyclohexanone is an important process to synthesis of caprolactam, which is an important raw material in the production of nylon. However, the industrial route suffered from the disadvantages such as harsh reaction conditions and low reactivity, therefore, selective oxidation of cyclohexane under mild conditions attracted great attention. Since photocatalysis has unique advantages in saturated C—H activation and oxidation, in this paper, a series of Bi₂O₃-TiO₂ composite photocatalysts were prepared by hydrothermal method. Their structure, morphology, optical and photoelectrochemical properties were characterized in detail by various techniques such as SEM, XRD, N₂ physical absorption and desorption, UV-Vis, photoluminescence spectroscopy, and transient photocurrent response. The photocatalytic performance of pure TiO₂, Bi₂O₃ and Bi₂O₃-TiO₂ composites toward selective oxidation of cyclohexane was compared under the reaction conditions of ambient temperature, 0.1 MPa of oxygen, and 500 W xenon lamp simulating solar light source. The results show that the catalytic activities of hybrid Bi₂O₃-TiO₂ composites are higher than that of pure TiO₂. Among them, 9%Bi₂O₃-TiO₂ exhibits the highest activity, the conversion is 13.32%, and the total selectivity (cyclohexanone and cyclohexanol) is 95.5%. The selectivity of cyclohexanone and cyclohexanol is 57.3% and 38.2%, respectively, and the ketone to alcohol ratio is 1.5. The characterization results confirm that the composite catalyst has a wider light absorption frequency range and can effectively promote the separation of photogenerated electrons and holes. In addition, the Bi₂O₃-TiO₂ composites possess higher specific surface area than pure TiO₂, which is conducive to increasing the concentration of surface active centers.