A ternary visible-light driven photocatalyst, Ag/BiVO4/reduced graphene oxide (rGO) composite was manufactured by hydrothermal strategy. The optimized products were characterized by XRD, SEM, HRTEM, EDS, XPS, DRS, Raman spectra, PL, BET, photocurrent density and EIS analysis. Compared to pure BiVO4, the fabricated ternary composite showed enhanced photocatalytic ability to decompose pollutant under visible light. Triclosan was completely removed after 100 min in solution with 1 mg/mL photocatalyst under visible light irradiation. Repeated cycle tests demonstrated the photo-stability and reusability of composite to decompose triclosan, indicating that this material could be utilized repeatedly. The upgraded photocatalytic ability was attributed to the addition of Ag and rGO, which enhanced the charge separation and inhibited the recombination of photogenerated electrons and holes. The EPR spin-trap technique (with DMPO) was performed to identify the radicals produced in Ag/BiVO4/rGO under the visible light, and trapping experiments were conducted to determine the main active species in the photocatalytic process of decomposing triclosan. Finally, seven reaction intermediates of triclosan were detected by LC-MS/MS and possible degradation routes were proposed.