Abstract <p>To develop photocatalytic oxidation of glucose to value-added chemicals, Bi₂MoO₆ incorporation with Bi has been prepared for conversion of glucose in water. The effects of Bi content and photocatalytic reaction conditions on the conversion of glucose has been further explored. The results indicated that arabinose and formic acid were the main products for photocatalytic glucose oxidation over the Bi/Bi₂MoO₆ nanohybrid. Compared to pure Bi₂MoO₆, the Bi/Bi₂MoO₆ nanohybrid exhibited superior photocatalytic activity and an increased total selectivity. Under optimal reaction conditions, the total selectivity of arabinose and formic acid reached up to 97% with 66% glucose conversion for Bi/Bi₂MoO₆ nanohybrid. The introduction of Bi not only significantly enhanced the generation of active species, but also effectively improved the adsorption capacity of glucose. Electron spin resonance spectra and scavenger experiments demonstrated that superoxide radicals and singlet oxygen played a crucial role in the photocatalytic oxidation of glucose.</p>