A novel plasmonic photocatalyst Ag/AgI was synthesized via a microwave-assisted irradiation synthesis in nonaqueous media. The sizes and shapes of the nanoparticles were strongly influenced by the microwave irradiation time and the concentration of polyvinylpyrrolidone (PVP) surfactant used in the reaction system. The Ag/AgI nanoparticles prepared using 0.3 mmol PVP at 140°C under microwave irradiation for 5 min possessed diameters of *100 nm. The photocatalytic reaction parameters, such as Ag/AgI catalyst loading amount, initial concentration of Rhodamine B (RhB) dye, solution pH, and photocatalysis temperature were investigated. The photocatalytic degradation of RhB followed a pseudo-first-order kinetic model, and the as-prepared plasmonic Ag/AgI photocatalysts exhibited strong photocatalytic activity and good durability for the degradation of RhB under visible light. Quenching experiments indicating that Á OH in solution, positive holes (h ? ), and adsorbed Á OH were the main reactive species in the system.