In the present work, novel isolated Ti-SBA-15-spherical and Ti-KIT-6 (Si/Ti = 200, 100 and 50) photocatalysts have been synthesized; optimized through N-2-adsorption/desorption, SEM, EDX, UV-Vis, FT-IR, XPS and TEM analysis techniques; and explored for the photocatalytic reduction of greenhouse gas CO2 to renewable fuels. The Ti-KIT-6 (Si/Ti = 100) showed better 0-14 production rate (4.15 mu mol gcat.(-1) h(-1)) than the corresponding Ti-KIT-6-dried (2.63 mu mol gcat.(-1) h(-1)) and the Ti-SBA-15-calcined/dried (1.85, 3.45 mu mol gcat.(-1) h(-1), respectively) in the initial optimization reactions. CH3OH, CO, and H-2 are the other main fuel products produced by the Ti-KIT-6-calcined (Si/Ti = 100). The increased surface concentration of OH groups found in the Ti-KIT-6-calcined (Si/Ti = 100) than the other two ratios (Si/Ti = 200, 50), the presence of more accessible surface reaction active sites due to the lower number of Ti-O-Ti or TiO2 agglomerates, and the more isolated Ti species which are uniformly dispersed on the 3-D KIT-6 mesoporous silica support without collapsing the mesoporous structure, have boosted the higher activity, which is even higher than the best commercial Aeroxide P25 TiO2. The reaction has been preceded by the competitive adsorption of CO2 and H2O vapors. The UV light source/intensity, H2O/CO2 ratios and catalyst shapes are the key factors that influence the performance of the catalyst, and therefore, these parameters have been optimized to boost the fuel products. (C) 2014 Elsevier B.V. All rights reserved.