Ag 2O/TiO 2 catalysts with varying amounts of Ag 2O 0.5, 1, 2, and 5 wt% loadings are prepared by impregnation method and Ag/TiO 2 catalyst is prepared by photo deposition method. These catalysts are characterized by XRD, SEM-EDAX, DRS, XPS and TEM techniques. DRS studies clearly showing the expanded photo response of TiO 2 into visible region on impregnation of Ag + ions on surface layers of TiO 2 due to the increased number of energy states created by the silver ions in TiO 2 surface lattice. TEM images are showing the fine dispersion of silver particles on TiO 2 surface. XPS of Ag 2O/TiO 2 calcined and used catalysts along with Ag 2O/TiO 2 reduced and Ag/TiO 2 photo deposited catalysts are compared and the binding energy values of Ti 2p, O1s and Ag 3d are confirming that silver ions are in interaction with TiO 2 in Ag 2O/TiO 2 calcined catalysts. EDAX analysis supports the presence of silver species on the surface layers of TiO 2. Photocatalytic hydrogen production activity studies are conducted over Ag 2O/TiO 2, Ag 2O/TiO 2 reduced and Ag/TiO 2 photo deposited catalysts in pure water and methanol:water mixtures under solar irradiation. Maximum hydrogen production of 145 μmoles/h is observed on 0.5wt% Ag 2O/TiO 2 catalyst in pure water and the maximum hydrogen production of 3350 μmoles/h is observed on 1wt% Ag 2O/TiO 2 catalyst in methanol:water mixtures. Whereas Ag 2O/TiO 2 reduced and Ag/TiO 2 photo deposited catalysts are not showing any hydrogen production activity either in water or in methanol:water mixtures under solar irradiation. Based on the XPS, DRS, TEM, SEM-EDAX studies and the hydrogen production activity on these catalysts, a structure–activity correlation has been proposed wherein the interacted Ag + ions on the surface layers of TiO 2 are playing an important role in maintaining the hydrogen production activity under solar irradiation.