Various Ti-containing HMS mesoporous molecular sieves having high surface areas and pore volumes have been prepared at ambient temperature. The Ti-HMS samples exhibited a well-defined XRD pattern of typical hexagonal lattice. UV-vis and XAFS spectral for the calcined forms of Ti-HMS indicated that the Ti ions are tetrahedrally coordinated in the framework of HMS for the samples of Ti-HMS(1) and Ti-HMS(2), while at least a fraction of Ti-oxides in Ti-HMS(10) is in octahedral coordination. UV irradiation of the Ti-HMS catalysts in the presence of NO was found to lead to the decomposition of NO to form N2, O2, and N2O at 273 K with different yields and product distributions. The photocatalytic performance of Ti-oxides appears to be completely modified by their incorporation structure and reaction environment. High efficiency and selectivity for the formation of N2 and O2 in the photocatalytic decomposition of NO was achieved with the Ti-HMS(1) having highly dispersed isolated tetrahedral titanium oxide species, while the reactivity decreased with an increase in the Ti content.