Hierarchical nano-crystalline TS-1 can be directly synthesized using tetrapropylammonium hydroxide (TPAOH) as single template in the presence of a 'seed' gel. The hierarchical nano-crystalline TS-1 was characterized by scanning electron microscopy, transmission electron microscopy, powder X-ray diffraction, UV-Vis diffuse reflectance spectroscopy and nitrogen adsorption-desoprtion. Compared with the conventional TS-1, the hierarchical nano-crystalline TS-1 contained an additional porosity including supermicro/mesopores, which attributed to the interstitial voids existing between the nanocrystals. The secondary porosity in the TS-1 material provided an enhanced external surface area and high mesopore volume in favor of fast diffusion of both reactants and products, which resulted in an enhanced activity in the epoxidation of bulky molecules cyclohexene using aqueous H(2)O(2) solution as oxidant. (C) 2011 Elsevier Ltd. All rights reserved.