In the current work an attempt has been made to synthesize novel high surface area nano-TiO 2 materials (titanium dioxide nanoparticles/TNPs and nanostructured or mesoporous titanium dioxide using KIT-6 silica template/Meso. TiO 2 ) in order to establish the photocatalytic reduction of CO 2 greenhouse gas in the presence of H 2 O vapor to produce hydrocarbons and syngas. The synthesized materials have been characterized through N 2 -adsorption/desorption, X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and ultraviolet–visible (UV–Vis) spectroscopy analysis techniques. The TNPs consists of an average 11nm of TiO 2 particles, shows a higher surface area of 151m 2 /g than the commercial Aeroxide P25 TiO 2 (53m 2 /g), and also demonstrates an enhanced adsorption capacity. However, the Meso. TiO 2 has shown a higher surface area (190m 2 /g) and mesoporosity (4nm pores) than the TNPs and Aeroxide P25 TiO 2 , as confirmed by the characterizations. In the reaction, the TNPs with the enhanced adsorption capability, due to the high surface area and smaller nano-sized particle morphology, showed a higher syngas (CO, H 2 ) production than the commercial Aeroxide P25 TiO 2 . However, the novel Meso. TiO 2 showed more hydrocarbons (CH 4 , CH 3 OH) and a higher syngas production together with better reaction kinetics and stability due to its better characteristics than the commercial Aeroxide P25 TiO 2 . The key parameters that affect the activity have been optimized to increase fuel production. The reaction mechanism indicates competitive adsorption of CO 2 and H 2 O vapors on the catalyst surface. The key parameters including the UV light source and UV intensity, H 2 O/CO 2 ratios and catalyst shapes influence the catalytic performance, and therefore, these parameters have been optimized to increase the fuel products. Partial saturation of the active adsorption sites and the oxygen produced are the possible causes of the deactivation, however, the catalysts can be regenerated quickly through a simple evaporation technique.