Ethylene and phenylene bridged polysilsesquioxane xerogels having amine and thiol groups attached to the surface have been obtained by the sol-gel method from 1,2-bis(triethoxysilyl)ethane or 1,4-bis(triethoxysilyl)benzene and functionalized silanes in the presence of an ammonium fluoride catalyst in an ethanol solution. The synthesized samples have a porous structure (700-850 m(2)/g) and a high content of functional groups (1.4-1.9 mmol/g). The obtained porous bridged polysilsesquioxanes exhibit a considerable affinity for adsorbing several organic compounds (n-hexane, n-heptane, benzene, cyclohexane, acetonitrile and triethylamine) from the gas phase. The sample with an ethylene bridge and amino groups in the surface layer has the highest uptake of all compounds. Data from adsorption measurements show that functionalized organosilicon materials can be used as effective adsorbents of organic contaminants from the gas phase. (c) 2007 Published by Elsevier B.V.