A series of organophilic montmorillonites (MMTs) modified with various alkyl siloxane amino oligomer groups have been synthesized and their properties were investigated. New organophilic MMTs containing siloxane amino oligomers with alkyl group instead of conventional alkyl amines were synthesized to improve thermal stability as well as gallery spacing. The organophilic MMTs were synthesized from MMT by utilizing the siloxane amino oligomers with various alkyl groups in the water/dioxane solution, which was performed without aq. HCl. Thermal decomposition temperature, gallery spacing, and hydrophobicity of synthesized organophilic MMTs were investigated. X-ray diffraction and TEM experiment results on new organophilic MMTs demonstrated that introduction of siloxane amine oligomers increased d-spacing between silicate layers. The decomposition temperatures of new organophilic MMTs measured by TGA was remarkably improved above 200℃ as compared with those of conventional alkyl substituted organophilic MMTs.