TiO2-based photocatalyst materials were synthesized through a sol–gel method, followed either by: (1) hydrothermal treatment (150 °C/24 h), or (2) heat treatment (calcination) in a temperature range between 400 and 900 °C. The resulting materials were characterized through BET, XRD, TEM, FTIR, RAMAN, laser diffraction and UV–Vis Diffuse Reflectance Spectroscopy. Photoactivity of the various materials was checked against photocatalytic water-splitting for hydrogen production and a relationship between TiO2 structure and hydrogen production capacity was identified. Optimum results were obtained for anatase-rutile mixtures in a ratio of 87:13. The activity of the home-made photocatalysts was also compared (under the same conditions) with the best commercially available materials which have been widely described in the literature: Hombikat UV100, Millenium PC100, Kronos vlp7000,Degussa P25and Kemira 625.