TixSiMCM-41 is a mesoporous photocatalyst with a tetragonal framework and high structural regularity. In this study, Ca was introduced to the TixSiMCM-41 surfaces to improve CO2 absorption. The catalytic performance of mesoporous Ca/TixSiMCM-41 was superior to that of the reported Ca/TixSiO2 nano-sized composite catalyst. The photoreduction of CO2 to CH4 improved remarkably over the Ca(10.0 wt.%)/Ti35Si65MCM-41 catalyst, producing 82.0 mu mol g(-1) cat L-1 after an 8 h reaction. A model for the enhanced photoactivity over Ca/TixSiMCM-41 was suggested, and the results were attributed to the effective charge separation and inhibited recombination of the photogenerated electron-hole pairs over Ca/TixSiMCM-41. (C) 2015 Elsevier B.V. All rights reserved.