Various pillared carbons consisting of silsesquioxane bridged graphene layers were prepared from the pyrolysis of silylated graphite oxides. Pillared carbons with interlayer spacings of 1.34-1.6 nm were obtained when prepared from graphite oxide silylated with alkyltrichlorosialne and then with methyltrichlorosilane. The graphene layers of pillared carbons were not well ordered when it was obtained from graphite oxide silylated with alkyltrichlorosialne and then with 3-aminopropyltriethoxysilane. The hydrogen excess adsorption of pillared carbons at ambient temperature reached 0.6 wt% and showed relatively high total hydrogen storage of 14 g/L at 20 MPa. Moreover, pillared carbon obtained from graphite oxide repeatedly silylated with methyltrichlorosilane showed a high adsorption heat of 8-11 kJ/mol. Copyright (C) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.