Organoclays synthesized with small organic cations can effectively adsorb hydrophobic organic compounds (HOCs), and the hydrophobic siloxane surfaces of clay minerals have been considered as the main adsorption sites for HOCs. Therefore, reducing charge density of clay minerals which can effectively increase the exposed siloxane surface areas has been generally used to enhance the adsorption capacity of organoclays towards HOCs. In this work, we will present a new method to increase the exposed siloxane surface areas of the synthesized organoclays and enhance their adsorption capacity. Firstly, the original inorganic cations on montmorillonite were exchanged with Li+, and then part of the Li+ (i.e., 20% to 60% of the montmorillonite’s CEC) were further exchanged with tetramethylammonium cation (TMA). After that ,the samples were heated at 200 ℃ for 12 h to make sure most of the Li+ were transferred to montmorillonite layers. With this method the layer charge of montmorillonite can be effectively reduced while the layered structure of montmorillonite will be preserved by pre-exchanged TMA. Finally, the remaining Li+ cations were further exchanged with TMA. The structural and adsorptive characteristics of the resulting organoclays were compared with those synthesized using traditional method (i.e., first reducing the charge density and then exchanging TMA). Organociates synthesized with small organic cations can effectively adsorb hydrophobic organic compounds (HOCs), and the hydrophobic siloxane surfaces of clay minerals have been considered as the main adsorption sites for HOCs. Thus, reducing charge density of clay minerals which can effectively increase the exposed siloxane Surface areas has been generally used to enhance the adsorption capacity of organoclays towards HOCs. In this work, we will present a new method to increase the exposed siloxane surface areas of the synthesized organclays and enhance their adsorption capacity. After that, the samples were heated at 200 ° C for 12 h to make (ie, 20% to 60% of the montmorillonite’s CEC) were further exchanged with tetramethylammonium cation (TMA) sure most of the Li + were transferred to montmorillonite layers. With this method the layer charge of montmorillonite can Finally, the remaining Li + cations were further exchanged with TMA. The structural and adsorptive characteristics of the resulting organoclays were compared with those synthesized using traditional method (ie, first reducing the charge density and then exchanging TMA).