Porous materials were obtained from clays by gallery templated synthesis. The equivalent surface areas of the samples were in the range 600–700 m 2 g À1 and the corresponding microporous volumes were near 0.3 cm 3 g À1 . HRTEM confirmed the lack of long-range order of the prepared samples. Low temperature nitrogen adsorption showed textural differences in the samples, namely those arising from the neutral amines of different chain length used in synthesis. The possibility of using such materials as adsorbents of volatile organic compounds, due to their textural and hydrophobic characteristics, was studied by the adsorption of ethanol and methyl ethyl ketone and water for comparison. Their potential use as adsorbents for the purification of methane, e.g., for upgrading natural or landfill gas, was also studied by the determination of the room temperature adsorption isotherms of carbon dioxide, ethane, methane and nitrogen, where high initial selectivity values were obtained for the methane/carbon dioxide separation.