Silico-aluminates (zeolites) have been recently utilized promisingly as the support for photocatalytic hydrogen production using solar-activated TiO2-based nanoparticles. Aside from conventional advantages offered by the supports in photocatalysis, we demonstrate the unique physicochemical impact of zeolites on photocatalytic hydrogen production. Beside zeolites, our synthesized materials comprise titanium dioxide (TiO2) as the semiconductor, cobalt ions as the hydrogen evolution sites, and heteropolyacids (HPAs) as the multifunctional solid acids with significant excitability under visible light. Four classes of zeolites (Na-Y, Na-mordenite, H-Y, and H-beta) with different Si/Al ratios and sodium contents were evaluated. Among the studied photocatalysts, Na-Y and Na-mordenite containing 10 wt% titania emerged as the potential candidates for the hydrogen evolution reaction, with corresponding rates of 250.8 and 187.2 mu mol/g h, in comparison to 84.2 mu mol/g h for Degussa P25; while these values for H-Y and H-beta were 96.8 and 100.1 mu mol/g h, respectively. The higher photocatalytic activity of the first two classes is attributed to the basicity of the zeolite matrix, which is possibly due to the pH dependency of the TiO2 band edges. The results indicate the importance of controlling the chemical properties of the zeolite as a photocatalyst support through the selection of suitable types. Furthermore, our analyses show that the precise pore size distribution of the zeolite framework rules over accommodating the impregnated species whether in the pores or on the surface. This ultimately enables a vast array of synthesis opportunities for development of the-state-of-the-art solar-activated photocatalysts based on earth-abundant materials. (C) 2014 Elsevier Ltd. All rights reserved.