The effect of the calcination conditions on the properties and catalytic performance of hierarchical ZSM-5 zeolite has been investigated using different reactions as catalytic tests: acylation of aromatic substrates and rearrangement of linear and cyclic epoxides. The hierarchical h-ZSM-5 material was prepared by crystallization of silanized protozeolitic units. The removal of the organics present in the as-synthesized ZSM-5 samples has been carried out using two different calcination procedures: (i) directly under air atmosphere; (ii) following a two-step (nitrogen-air) treatment. Clear differences are noticed related to the textural properties of the ZSM-5 samples, since the h-ZSM-5 presents higher BET and external surface area than standard ZSM-5 zeolite. Whereas the calcination method does not affect the properties of the reference ZSM-5 sample, noticeable changes were observed over the hierarchical zeolite. The concentration of Bronsted acid sites decreases by half for one-step air calcination, but only a quarter when using a two-step nitrogen/air calcination, showing that the aluminium present in hierarchical ZSM-5 is very sensitive to the calcination conditions as it may undergo framework extraction and dehydroxylation phenomena. For all the studied reactions, the hierarchical sample, calcined by a two-step treatment, presents higher activity than when using direct air calcination. (C) 2011 Elsevier B.V. All rights reserved.