This work focused on hydrogen production from the photocatalytic water splitting under visible light irradiation using Eosin Y-sensitized mesoporous-assembled TiO2-SiO2 mixed oxide photocatalysts, of which the mesoporous-assembled TiO2-SiO2 mixed oxides with various TiO2-to-SiO2 molar ratios were synthesized by a sol-gel process with the aid of a structure-directing surfactant. The effects of SiO2 content, calcination temperature, and phase composition of the mixed oxide photocatalysts were investigated. The experimental results showed that the TiO2-SiO2 mixed oxide photocatalyst with the TiO2-to-SiO2 molar ratio of 97:3 and calcined at 500 degrees C provided the maximum photocatalytic hydrogen production activity. The characterization results supported that the 0.97TiO(2)-0.03SiO(2) mixed oxide photocatalyst (with the suitable SiO2 content of 3 mol%) possessed superior physicochemical properties for the photocatalytic reaction as compared to the pure TiO2, particularly higher specific surface area, lower mean mesopore diameter, higher total pore volume, and lower crystallite size, which led to an enhanced photocatalytic activity. Copyright (c) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.