Novel Bi4O5Br2 nanoflakes with a thickness of approximately 5 nm and a band gap energy of 2.54 eV were synthesized by a rapid and energy-saving microwave route. Under blue light emitting diode (LED) irradiation and using the Bi4O5Br2 nanoflakes as a photocatalyst, selective catalytic oxidation of benzyl alcohol (BA) into benzaldehyde (BAD) was successfully achieved with a high selectivity and conversion ratio. Compared to Bi12O17Cl2, which has a similar blue LED light absorption capability and a band gap energy of 2.37 eV, these Bi4O5Br2 nanoflakes exhibit superb conversion efficiency (>99%) and selectivity (>99%) toward the photocatalytic oxidation of BA into BAD. Based on the structural characterization of the as-synthesized photocatalyst, comparison of photocatalytic performances, investigation of active radicals, and quantum chemical calculations, a possible photoreaction pathway is explored and proposed. It is revealed that the high selectivity of the system comes from direct hole oxidation of alkoxide anions (BA(-)) and the appropriate valence band potential (+2.41 V vs. NHE) of Bi4O5Br2. And the high conversion ratio is attributed to the positively charged surface, large specific surface area with micro-nano structures, and effective separation of photogenerated carriers of the as-synthesized photocatalyst. In addition, the as-synthesized Bi4O5Br2 catalyst remains stable during the photocatalytic conversion process and can be utilized repeatedly, suggesting its potential for practical applications. (C) 2016 Elsevier B.V. All rights reserved.