Bi2WO6 nanoparticles doped with Ag, and modified with Ag nanoparticles, were successfully prepared using a two-step microwave assisted and hydrothermal synthesis. With Ag doping, the Bi ions were substituted by the dopant Ag ions in the host lattice structure of Bi2WO6. With Ag nanoparticles modification, the Ag nanoparticles grew on the surface of the Bi2WO6 nanoparticles without changing the host lattice structure. The photocatalytic activities of the samples were studied by visible light irradiation of rhodamine B. Both the Ag doping and the Ag nanoparticles modification enhanced the photocatalytic activity of the Bi2WO6 nanoparticles. Moreover, Ag nanoparticles modification produced a more than two times higher enhancement of the photocatalytic activity than the Ag doping method. Furthermore, a mechanism of the significant photocatalytic activity enhancement by Ag nanoparticles modification is proposed.