Ni/Fe bimetallic nanoparticles were synthesized using biochar as a support (BC@Ni/Fe) and their effectiveness in removing BDE209 from soil was investigated. BET, SEM, TEM, XPS and FTIR were used to characterize the catalyst, and the efficiencies of biochar, Ni/Fe nanoparticles and BC@Ni/Fe for removing BDE209 from soil were compared. The results showed that Ni/Fe bimetallic nanoparticles highly dispersed in the biochar, reducing its agglomeration. Thus, the reaction activity of BC@Ni/Fe was increased. The removal efficiency of BDE209 by BC@Ni/Fe was 30.2% and 69% higher than that by neat Ni/Fe and biochar, respectively. Meanwhile, an enhanced degradation efficiency of PBDEs in soil was realized by monitoring the formation of Br- ions with time in the system. In addition, the degradation products identified by GC-MS showed that the reductive degradation of BDE209 proceeded through stepwise or multistage debromination, for which the degradation pathways and removal mechanisms were speculated. Furthermore, BC@Ni/Fe reduced the bioavailability of metals in soil and adsorbed the degradation products of BDE209, representing an improvement over neat Ni/Fe nanoparticles for the remediation of PBDEs-contaminated soil. (C) 2016 Elsevier B.V. All rights reserved.