Polybrominated biphenyls (PBBs) are a group of new persistent organic pollutants, which have high toxicity and long-term bioaccumulation, and cause potential risks to human beings and aquatic ecosystem. Self-assembled dumbbell-like Fe3O4 was synthesized via ethylene-glycol mediated method to degrade PBBs, using BB209 as a model compound. The results showed that the growth process of dumbbell-like Fe3O4 precursor had two stages involving a fast nucleation of amorphous primary particles followed by a slow aggregation and crystallization of primary particles. Dumbbell-like Fe3O4 showed high activity for degradation of BB209 at the reaction time of 30 min with the degradation efficiency of nearly 100% at 300 degrees C. A whole series of nonabromobiphenyl to monobromobiphenyl and biphenyls were detected as the degradation products of BB209 by dumbbell-like Fe3O4, indicating the occurrence of successive hydrodebromination reaction. Furthermore, the amounts of three NoBB isomers followed the order of BB207 > BB208 > BB206, indicating that the reactivity of C--Br of BB209 was in order of meta- > para- > ortho-positions.