Mesoporous materials such as Ti-HMS, prepared at ambient temperature, were studied both under continuous flow and closed reaction systems for the photocatalytic decomposition of NO. The results indicate Ti-HMS to be a good photocatalyst with a continuous reactivity under prolonged irradiation. The direct decomposition of NO into N-2, O-2, and N2O at 275 K with a high selectivity for N-2 and O-2 in a closed system is noteworthy. In situ photoluminescence and EXAFS investigations show that the Ti exists in a tetrahedral coordination and is highly dispersed within the mesoporous material. The TPD studies, before and after the photocatalytic investigations, clearly indicate that NO molecules cannot be adsorb strongly on the surface of Ti-HMS photocatalysts, in contrast to the powdered TiO2 photocatalysts, where strong NO adsorption species have been observed. It is likely that the charge transfer excited state of the tetrahedrally coordinated titanium oxide species plays a significant role in the direct decomposition of NO.