The combination of zerovalent metal with a catalytic second metal ion (bimetallic materials) to enhance the dechlorination efficiency and rate of chlorinated compounds has received much attention. Bimetallic materials not only enhance the dechlorination process but also alter the reduction pathway and product distribution. In this study, the efficiency and rate of tetrachloroethylene (PCE) dechlorination by metal-modified zerovalent silicon was investigated as a potential reductant for chlorinated hydrocarbons under anoxic conditions. The X-ray photoelectron spectroscopic (XPS) results showed that metal ions including Ni(II), Cu(II), and Fe(II) could be reduced to their zerovalent forms on the Si surface. The dechlorination of PCE obeyed the pseudo-first-order kinetics, and the pseudo-first-order rate constants (k(obs)) for PCE dechlorination followed the order Ni/Si > Fe/Si > Cu/Si. Addition of Cu(II) lowered the dechlorination efficiency and rate of PCE by Si, while the k(obs) values for PCE dechlorination in the presence of 0.1 mM Fe(II) and Ni(II) were 1.5-3.8 times higher than that by Si alone. In addition, the efficiency and rate of PCE dechlorination increased upon increasing the mass loading of Ni(II) ranging between 0.05 and 0.5 mM and then decreased when the Ni(II) loading was further increased to 1 mM. The scanning electron microscopic (SEM) images and electron probe microanalytical (EPMA) maps showed that the Ni nanoparticles deposited on the Si surface and aggregated to a large particle at 1 mM Ni(II), which clearly depicts that the Ni(II) loading of 0.5 mM is the optimal value to enhance the efficiency and rate of PCE dechlorination by Si. Also, the reaction pathways for PCE dechlorination changed from hydrogenolysis in the absence of Ni(II) to hydrodechlorination when Ni(II) concentrations were higher than 0.05 mM. Results obtained in this study reveal that the metal-deposited zerovalent silicon can serve as an environmentally friendly reductant for the enhanced degradation of chlorinated hydrocarbons for long-term performance.