Hierarchical mordenites were prepared by a sequential post-treatment method based on a commercial mordenite with a Si/Al molar ratio of 15. The mordenite obtained by acid treatment showed much higher catalytic activity than the parent mordenite in the benzylation of benzene with benzyl alcohol, even a little better than that obtained by acid-base treatment. The apparent reaction rate constant for acid-leached mordenite is six times higher than that for HM. Further, the mordenite with acid-base-acid treatment exhibited the highest catalytic activity among these samples. The apparent reaction rate constant for acid-base-acid-leached mordenite is 15 times that for HM and twice that for acid-leached mordenite and acid-base-leached mordenite. This remarkably enhanced catalytic performance should be attributed to more accessible acid sites and much better mass transfer ability from rich mesoporosity in acid-base-acid-leached mordenite. (C) 2013 Elsevier Inc. All rights reserved.