A new porous benzene-silica hybrid clay heterostructure has been prepared by a template-assisted method. The synthesis of Hybrid Porous Clay Heterostructures (HPCH) has been performed via the intercalation of a quaternary ammonium cation surfactant (cetyltrimethylammonium bromide) and a neutral amine (octylamine) as cosurfactant, in a Portuguese clay, to direct the interlamellar hydrolysis and condensation polymerisation of neutral inorganic tetraethylorthosilicate (TEOS) together with an organic precursor, the 1,4-bis(triethoxysilyl)benzene (BTEB). The material has been characterised by elemental analysis, powder X-ray diffraction, nitrogen adsorption, C-13 CP MAS, Si-29 MAS and CP MAS NMR spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy (SEM) and thermal analyses. The hydrophobicity of the material was tested by water adsorption. Its potential application as adsorbent of volatile organic compounds was studied by the adsorption of methanol, methyl ethyl ketone, toluene and trichloroethylene.