Photocatalytic oxidation has been widely employed in organic synthesis, by virtue of the green, mild and simple reaction conditions as well as high selectivity. Introducing oxygen vacancies (OVs) with proper concentrations into the photocatalysts has been proven as an effective strategy to boost the catalytic performances. However, the currently used treatment method under high temperature at reducing atmosphere inevitably introduces a large number of OVs at the interior of the catalyst and serving as the recombination centers of carriers. To address this issue, here we develop a facile solvothermal process to prepare ultrathin BiOBr nanosheets with rich surface OVs. This method effectively decreases the bulk of the material and the ratio of interior OVs, rendering most of the OVs exposed on the surfaces which act as exposed catalytic sites and enhance the separation of carriers, therefore significantly elevates the photocatalytic performances. For the photo-oxidation reaction of secondary amines, under the conditions of visible light, ambient temperature and atmosphere, the BiOBr nanosheets featuring rich surface OVs deliver a doubled conversion compared to those with low OV concentrations, and a high selectivity of 99%, a high stability as the performance shows no reduction after 5 times of circular reaction.