Sulfidated and bimetal modification can improve the reactivity and selectivity of zero-valent iron in contaminant removal. However, previous studies were focused on unilateral material approaches. In this article, a new hybrid composite Ag/S-ZVI was prepared by doping elemental silver on surface of sulfidated nanoscale zerovalent iron (S-nZVI). The results of X-Ray Diffraction (XRD), energy dispersive spectrometer (EDS) and X-ray Photoelectron Spectroscopy (XPS) indicated Ag was dispersed on the surface of S-nZVI. Scanning electron microscope (SEM) images displayed Ag/S-ZVI was irregular clusters with rough surfaces, small agglomeration, and quasi-spherical in shape. The removal of TCE by Ag/S-ZVI was 90.4% within 20 min. The reaction rate constant <i>K<sub>obs</sub></i> of Ag/S-ZVI was 2.59 times or 1.85 times of nZVI or S-nZVI, respectively. Cycling experiments showed that Ag/S-ZVI had good recycling ability, and the removal rate of TCE reached 72.6% at the third cycle. The addition of Ag<sup>+</sup> makes S-nZVI as an abundant and efficient source of reducing electrons. The Fe<sup>0</sup> core can break C-Cl bonds by releasing electrons and the surface layer of Ag favors the transfer efficiency of electrons. Such study provides an efficient and robust ternary system for the remediation of TCE in groundwater.