Ag species/TiO 2 nanoflakes photocatalysts with different relative contents (Ag + , Ag 2+ , Ag 0 ) have been successfully synthesized by a simple template-free synthetic strategy. X-ray photoelectron spectroscopy, X-ray diffraction, and UV–vis diffuse reflectance spectra indicated that the dopant ions (Ag + or Ag 2+ ) were partly incorporated into the titanium dioxide nanoflakes. Meanwhile, part of the silver ions migrated to the surface after the subsequent calcination and aggregated into ultra-small metallic Ag nanoclusters (NCs) (1–2nm), which are well dispersed on the surface of TiO 2 nanoflakes. The photocatalytic activities of the Ag species/TiO 2 materials obtained were evaluated by testing the photodegradation of the azo dye reactive brilliant X-3B (X-3B) under near UV irradiation. Interestingly, it was found that the maximum photocatalytic efficiency was observed when Ag species coexisted in three valence states (Ag + , Ag 2+ , Ag 0 NCs), which was higher than that of Degussa P25. The high photocatalytic activity of the Ag species/TiO 2 can be attributed to the synergy effect of the three Ag species.