Through a simple grinding method, AgI/TiO2 composites were successfully synthesized. The as-prepared AgI/TiO2 composites were used as photocatalysts for Rhodamine B (RhB) degradation under visible light irradiation and exhibited excellent photocatalytic performance. In the presence of composites, almost 100% RhB was decomposed after 60 min. The photocatalytic activity of AgI/TiO2-0.5 composite was optimal, which was 9.5 times higher than that of pristine TiO2, and 15.6 times higher than that of AgI. Moreover, experimental results revealed that the improved photocatalytic activity was not only ascribed to the loading AgI but also resulted from the method that enabled the exposure of more active sites in the composites. In addition, the intimate interfacial contact obtained by this method could also promote the efficient separation of photogenerated electron-hole pairs. Moreover, the possible photocatalytic active species and the stability of the photocatalyst were investigated in detail.