A lamellar titanosilicate (LTS-1) was hydrothermally synthesized by employing a bifunctional surfactant as the structure-directing agent (SDA). Highly crystalline LTS-1 was obtained at an optimal SDA/Si molar ratio of 0.04. As-synthesized LTS-1 possessed a multilayer structure, which was constructed from a collection of 2-nm zeolite nanosheets and interlayer SDA molecules. Removing the intercalated organic species induced irregular layer stacking to a certain extent, leading to intracrystal mesopores of ca. 3.2 nm in diameter. The catalytic performance of LTS-1 was investigated in the epoxidation of various bulky alkenes with tert-butyl hydroperoxide, cumene hydroperoxide, or aqueous H2O2. LTS-1 was more active than conventional titanosilicates for reactions involving bulky alkenes and oxidants, and it was immune to Ti leaching and irreversible deactivation. (C) 2012 Elsevier Inc. All rights reserved.