A one pot and environmentally benign synthetic route for plasmonic photocatalytic Ag@AgCl nanoparticles in a PVA-dissolved aqueous solution system is presented. The synthesized AgCl has a cubic-shape and its edge length can be controlled from ∼57 to ∼170 nm by varying the reaction temperature. In this system, PVA was used as a stabilizer for the formation of Ag@AgCl nanoparticles through interaction with Ag+ ions. After partial reduction with L-arginine, the metallic Ag is formed on the surface of the AgCl substrates and the contents of the metallic Ag mainly affect both the visible-light absorption properties and the plasmonic photocatalytic efficiency of the Ag@AgCl nanocomposites. A plausible growth mechanism of metallic silver during the reduction process is proposed. More importantly, it is verified that the size of the AgCl substrate affected the light absorption region of the Ag@AgCl nanocomposite.