The efficiency of photocatalytic water splitting for TiO2 dispersed on four SiO2 aperiodic porous supports is discussed in this work. The four TiO2-SiO2 composite materials were prepared via a sol-gel method and then subjected to supercritical drying, natural drying, rotatory vapor drying, or hydrothermal synthesis and the materials were subsequently calcined under identical conditions. These synthetic strategies result in differences in textural properties (specific surface area, pore diameter etc.) and in the amount of tetrahedrally coordinated Ti4+ ions. The TiO2-SiO2 materials were thoroughly characterized by powder X-ray diffraction (XRD), UV-Vis diffuse reflectance spectra (DRS), nitrogen adsorption studies, FT-IR spectroscopy, transmission electron microscopic (TEM) studies, and electron paramagnetic resonance (EPR) studies. The photocatalytic activity for hydrogen production is maximum when the amount of tetrahedrally coordinated Ti4+ ions is high. Thus, this work provides guidance towards the preparation of photoactive materials for generating hydrogen from water. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.