In recent years, BiVO4 has drawn much attention as a novel photocatalyst given its excellent ability to absorb visible light. This work reports the development of Ag-modified BiV1-xMoxO4 composites through a facile hydrothermal synthesis with the subsequent photoinduced reduction of Ag+ at almost neutral pH conditions. Metallic Ag nanoparticles were deposited on the (040) facet of Mo-doped BiVO4 powders. The crystal structure and morphology of the as-prepared samples were studied by XRD and SEM analyses. Moreover, the photocatalytic performance of BiVO4, Ag/BiVO4, and Ag-modified BiV1-xMoxO4 were evaluated by the degradation of rhodamine B (RhB). The Ag/BiV0.9925Mo0.0075O4 composite exhibited the most efficient photocatalytic performance. The present work provides greater insight into the application of BiVO4 in the field of photocatalysis.