Reduced graphene oxide (rGO) is a promising support for electrochemical and environmental applications. However, the role of rGO in dechlorination of chlorinated hydrocarbon by zerovalent iron-based nanoparticles remains unclear. Herein, the rGO-supported bimetallic Fe/Ni nanocomposites were fabricated by chemical reduction method and the microstructures as well as the electrochemical properties of rGO/Fe/Ni, were investigated to elucidate the dechlorination behaviors of trichloroethylene (TCE) under various environmental conditions. Results show that the 10-60 nm Fe/Ni nanoparticles with average particle size of 32 nm are homogeneously dispersed onto the rGO surface. The rGO/Fe/Ni exhibits excellent dechlorination efficiency and rate of TCE is 2.4 times higher than that of free Fe/Ni nanoparticles. Cyclic voltammetric curves and electrochemical impedance spectra indicate that the superior dechlorination activity is attributed to the strong interaction between Fe/Ni and rGO, low internal resistance and rapid diffusion rate of electrons and ions. In addition, the capacitive behavior of rGO can store and transfer 2.7-3.4 electrons produced from Fe-0 to the adsorbed TCE more readily, and then converts TCE to non-toxic ethane via hydrodechlorination in the presence of Ni nanoparticles. The rGO/Fe/Ni can be recycled for at least 8 times to effective dechlorinate TCE. Moreover, the reaction rate of TCE dechlorination can be enhanced 1.26-1.49 times when 5-10 mg L-1 humic acid are added. Results obtained in this study have clearly unveiled the role of rGO in hydrodechlorination of TCE and can provide a new insight into the development of rGO-supported bimetallic Fe/Ni nanoparticles for the enhanced removal of chlorinated pollutants in water and wastewater treatment.