Novel hexagonal Periodic Mesoporous Organosilicas (PMOs) and Disordered Mesoporous Organosilicas (DMOs) were synthesized by hydrolysis of 1,4-bis(trialkoxylsilyl) benzene precursor in alkaline aqueous solutions of different alkyl-trimethyl ammonium cations and evaluated for their hydrogen storage capacity. The PMO materials exhibit regular hexagonal pore arrangement and specific surface area between 640 and 782 m(2) g(-1) whereas the DMO materials have specific surface area that lies between 650 and 910 m(2) g(-1). The storage capacity of the materials is discussed in terms of number of molecules per surface unit. The materials exhibit a reversible hydrogen excess surface adsorption capacity up to 2.10 wt% at 6 MPa and 77 K. DFT calculations were performed to define the binding strength of hydrogen with the pore walls indicated an interaction energy value of -0.55 Kcal mol(-1), higher than the interaction energy value of hydrogen with a single benzene or a benzene incorporated in the IRMOR-1 walls. Grand Canonical Monte Carlo (GCMC) simulations showed that no hydrogen molecule can be inserted inside the wall structure of the materials. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.