Highly efficient TiO₂ photocatalysts (TiO₂/Ag-Ag₂O) co-modified by Ag as electron cocatalysts and Ag₂O as interfacial catalytic active sites were synthesized via a two-step process including the initial photoinduced deposition of metallic Ag nanoparticles on the TiO₂ surface (TiO₂/Ag) and the following in situ oxidation of partial Ag into Ag₂O by low-temperature calcination. Ag nanoparticles function as effective electron cocatalysts for the steady capture and rapid transportation of photogenerated electrons from TiO₂ surface to Ag₂O, while the adsorbed H⁺ ions from solution to Ag₂O as the interfacial catalytic active sites are reduced into H₂. The synergistic effect of Ag and Ag₂O can accelerate the electrons transfer and promote the rapid H₂-evolution reaction for enhanced photocatalytic H₂-evolution performance of TiO₂/Ag-Ag₂O. The highest H₂-evolution rate of the resultant TiO₂/Ag-Ag₂O calcinated at 300 ℃ reached 75.20 μmol/h, which was higher than those of the TiO₂ (3.59 μmol/h) and TiO₂/Ag (41.13 μmol/h) by 21.0 and 1.8 times, respectively. This study provides a new strategy for the design and synthesis of highly efficient photocatalytic H₂-evolution materials.