Ag/SmVO4 composite photocatalysts were synthesized and characterized by BET, XRD, Raman, SEM, TEM, XPS and DRS techniques. Their photocatalytic activities were determined by oxidative decomposition of RhB in aqueous solution under visible light irradiation. The charge separation efficiency was evaluated by the photocurrent-time and ֹOH-trapping experiments. The results revealed that the loaded Ag species greatly improved the efficiency in charge separation, and thus led to enhanced photocatalytic activities compared with that of the pure SmVO4. The sample contained 0.5 wt% Ag and heated at 500°C presents the highest photoactivity.