Visible light photocatalysis of Ag/AgCl/BiVO4 was synthesized by the selective doping of Ag/AgCl on (040) facet of monoclinic BiVO4. The as-prepared catalyst was characterized by XRD, SEM, EDS, UV-Vis DRS, XPS, and nitrogen adsorption studies. The photocatalytic activity of Ag/AgCl/BiVO4 was tested on the removal of a pharmaceutical drug carbamazepine (CBZ). A CBZ removal of 70.6% and COD and TOC decrements of 21% and 9.6% were achieved within a reaction time of 4 h. The results demonstrated that the addition of oxidants improved the photocatalytic activity (97.9% and 100% CBZ removal in the presence of H2O2 and PS). Photocatalytic mechanism of the Ag/AgCl/BiVO4 plasmonic composite photocatalyst under visible LED light irradiation was clarified and O-2(center dot-) radicals were found as the most dominant radicals. The toxicity decrement was 21.7% for the treated CBZ solution. Furthermore, the Ag/AgCl/BiVO4 heterostructured photocatalyst has high stability under visible light irradiation which could be reused after three consecutive runs with a small Ag leaching (< 0.1 ppm).