Titanium-rich highly ordered mesoporous silica has been synthesized by using unconventional Ti source TiCl4 under strongly acidic pH condition in the presence of a cationic surfactant as supramolecular structure directing agent (SDA). The most Ti-rich sample for these mesoporous titanium silicates with two-dimensional hexagonal ordered structure was observed with Si/Ti = 7.6 in the product. XRD, N-2 sorption, Si-29 MAS NMR, UV-vis diffuse reflectance, FT-IR spectroscopic tools, TEM and SEM image analyses were employed to characterize these materials. BET surface area and mesopore volume for all the samples were high. Strong UV-vis absorption band at 222 nm and Fr-IR stretching vibration band of Si-O-Ti at 956 cm(-1) were observed in these Ti-rich samples indicating the presence of titanium in isolated tetrahedral environment and strongly bound inside the mesoporous framework. These Ti-rich ordered mesoporous titanium silicate samples showed excellent catalytic activity in the epoxidation of styrene (sample 2 having Si/Ti = 7.6 showed 86% conversion with ca. 85% selectivity for styrene oxide) using dilute aqueous H2O2 as oxidant. (c) 2006 Elsevier Ltd. All rights reserved.