Polybrominated diphenyl ethers (PBDEs) have aroused highly environmental concerns because of their toxicity and ubiquitousness in the biological and environmental system. Here, we report that decabromodiphenyl ether (BDE209) undergoes efficient reductive debromination reaction by pyruvate under UV irradiation (>360 nm). The photoreductive degradation kinetics of BDE209 has been further investigated under different reaction conditions. The debromination reactions occur in a stepwise process, producing a series of lower brominated congeners. The debromination shows unconspicuous position-selective property. The possible photoreductive mechanism has been proposed by UV-vis and kinetic isotope effect (KIE). This study not only provides a potential application of removal of PBDEs contaminations but also provides some information for the fate of PBDEs in environment. (C) 2014 Elsevier B.V. All rights reserved.