The present study was carried out to better understand the reactivity of nanoscale Ni/Fe particles towards the dechlorination of polychlorinated biphenyls (PCBs) contained in waste capacitor oil and the corresponding dechlorination mechanism in subcritical water. Batch experiments showed that nanoscale Ni/Fe particles could more quickly and effectively dechlorinate PCBs stepwise as compared to nanoscale zerovalent iron (n-ZVI) and nano-Ni-0. The dechlorination products were much more centralized in the presence of Ni/Fe than other particles, and biphenyl, cyclohexyl-benzene and 1-alkyl-benzenes were the main products which can be used as raw chemicals. Moreover, catalytic hydrogenation by virtue of introduction of Ni-0 as catalyst can not only result in rapid dechlorination but also avoid formation of toxic chlorinated hydrocarbons. The reactivity of nanoscale Ni/Fe can retain in subcritical water for rapid catalytic hydrodechlorination. This process poses the prospect of recovery of valuable chemicals in the course of disposal of hazardous PCB-containing capacitor oil or transformer oil. (C) 2011 Elsevier B.V. All rights reserved.