Hierarchical Beta zeolite with mesoporous/microporous structure was synthesized by employing a bifunctionalized amphiphilic surfactant. N-2 adsorption-desorption isotherms indicated the presence of hierarchical mesopores in this sample. Transmission electron microscopy images confirmed the co-presence of ordered micropores and hierarchical mesopores. This sample exhibited excellent hydrothermal stability. In addition, the prepared hierarchically structured Beta zeolite showed greatly enhanced catalytic activity as compared with conventional counterpart for probe reaction involving large molecules due to the highly mesoporous structure, in which diffusion constraints of reactant molecules are the main concern. Such hierarchical micro/mesostructure Beta zeolite combined good hydrothermal stability and high activities may find potential applications in catalysis and adsorption involving bulky molecules. Crown Copyright (C) 2013 Published by Elsevier B.V. All rights reserved.