Selective photooxidation of toluene to benzaldehyde using O-2 as an oxidant has the advantages of mild reaction conditions and excellent atomic economy, but it often suffers from low conversion efficiency. To promote the photooxidation process, we fabricated iron-doped Bi2WO6 microflowers by a simple hydrothermal method to boost the formation of oxygen vacancies. The rich presence of oxygen vacancies not only accelerates the separation of photogenerated charge carriers but also enhances O-2 activation for center dot O-2(-) generation. Besides the slight improvement of Bi2WO6 stability, the Fe-doped Bi2WO6 displays enhanced activity and selectivity for benzaldehyde generation from toluene under visible light. This work illustrates a simple strategy for successful modulation of Bi2WO6 for improved performance in the photocatalytic selective oxidation processes.