It has been known that the intercalation of long alkyl chains in montmorillonites (MMT) increased the hydrophobicity as well as gallery spacing of UT, which has influenced on the exfoliation behavior of various polymers. A series of organophilic MMTs were synthesized from the water/isopropyl alcohol solution of MMT with ammonium salts of various alkyl amines. The properties of obtained MMTs such as thermal decomposition temperature, gallery spacing as well as hydrophobic property were investigated. The X-ray diffraction experiments on organophilic montmorillonite demonstrated that the increase of length of alkyl substituent resulted in increase in the spacing between silicate layers, which was ranged from 13.1 to 29.4 $AA$. On the other hand, introduction of (di-, tri-) alkyl substituents in ammonium salts decreased water absorption of organophiplic montmorillonite to 2.7%.