Photocatalytic selective oxidation of alcohols into high value-added carbonyl compounds accompanied by producing hydrogen peroxide (H2O2) is undoubtedly a more efficient solar energy conversion strategy with high atom economy. Herein, we have developed an efficient photocatalyst of bismuth-molybdate (Bi2MoO6) hierarchical hollow microspheres with tunable surface oxygen vacancies (OVs) for promoting the photocatalytic selective alcohol oxidation with H2O2 production. The effect of surface OVs on the photocatalytic efficiency is studied systematically by comparing the performance of different photocatalysts. The benzaldehyde and H2O2 production rates over the OV-rich Bi2MoO6 photocatalyst reach up to 1310 and 67.2 mu mol g(-1) h(-1), respectively, which are 2.3 and 4.0 times those generated from the OV-poor Bi2MoO6 hollow microspheres. The roles of various active radicals in the photocatalytic reaction are probed by a series of controlled experiments and in situ ESR measurements, revealing that both superoxide radical (center dot O-2) and carbon-centered radical are the key active intermediates. The introduction of surface OVs on Bi2MoO6 hollow microspheres accelerates the separation and transfer of photo-generated charge carriers as well as enhances the adsorption and activation of reactant molecules, thereby greatly promoting the photocatalytic selective oxidation of alcohols along with H2O2 production. This work not only demonstrates a facile strategy for the preparation of high-efficiency photocatalysts by simultaneous modulations of morphology and surface defects, but also offers insight into developing the dual-functional photocatalytic reactions for the full utilizations of photoinduced electrons and holes. (C) 2021 Elsevier Inc. All rights reserved.