The photocatalytic valorization of glucose has attracted more and more attention for producing value-added chemicals. Herein, value-added chemicals like arabinose and formic acid were obtained by selective photocatalytic oxidation of glucose irradiated with visible light, which was realized using Bi2O3/TiO2 composite as the photocatalyst and atmospheric O2 as the oxidant in water. It was found that the photocatalytic performance of Bi2O3/TiO2 composite in the glucose oxidation was obviously superior to that of pure Bi2O3 and pure TiO2, the significantly enhanced photocatalytic efficiency was mainly attributed to the promotion of photogenerated charge separation and adsorption capacity towards glucose. The influences of mass ratio of Bi2O3 to TiO2 and initial concentration of glucose on the glucose oxidation were further investigated with many details. Additionally, recycling experiments showed that the Bi2O3/TiO2 composite exhibited a favorable stability in the photocatalytic process, and the roles of various active species for glucose oxidation were also determined by the active species trapping experiments. This work could provide some valuable viewpoints for producing value-added chemicals from biomass by photocatalysis.