The transition of interlayer arrangement of HDTMA from lateral monolayer to zigzag arrangement or lateral bilayer when the montmorillonite possesses more negative surface charge were better accomplished. Regarding nature of interaction forces between montmorillonite and HDTMA at room temperature, it has been seen HDTMA + cations can faster intercalate than HDTMA-Br between the montmorillonite layers. It could be deduced that increasing the duration of modification time some electrostatic adsorption forces were lost and substituted by the hydrophobic adsorption forces due to the rearrangement of cations between montmorillonite layers. At higher temperature kinetics of electrostatic interaction of HDTMA + cations with montmorillonite changed compare to that at room temperature and a slight increase in the amount of cations adsorbed was occurred by increasing the duration of modification showing the importance of temperature in the kinetics of interaction mechanism of HDTMA and montmorillonite. The X-ray diffraction, Fourier transform infrared spectroscopy, and thermal gravimetric analysis was used to characterize the kinetics of modification of montmorillonite with HDTMA. The results showed that in the ratio of HDTMA/CEC of montmorillonite at 0.62 three arrangement of HDTMA could be formed: lateral monolayer, zigzag arrangement, and lateral bilayer. The transition of formation of HDTMA from lateral monolayer to zigzag arrangement or lateral bilayer was kinetically occurred when the montmorillonite had more positive charges on the edges and surfaces. Regarding the nature of interaction forces between montmorillonite and HDTMA (at room temperature) the rate of intercalation of HDTMA + cations was faster than that of HDTMA-Br molecules. However by increasing the duration of modification some electrostatic adsorption was lost and substituted by the hydrophobic adsorption due to the rearrangement of cations in between montmorillonite layers. At higher temperature kinetics of electrostatic interaction of HDTMA + cations with montmorillonite changed compare to that at room temperature and a slight increase in the amount of cations adsorbed was occurred by increasing the duration of modification showing the importance of temperature in the kinetics of interaction mechanism of HDTMA and montmorillonite.