Intercalation of octadecylamine (ODAMIN) into Na montmorillonite based on the ion-dipole interaction was investigated using molecular mechanics and molecular dynamics simulations combined with X-ray powder diffraction. Molecular modeling revealed the interlayer structure of the ODAMIN-montmorillonite intercalate, the charge distribution on the host layer and guest species, and the energy characteristics, i.e., the total sublimation energy and it's individual contributions (electrostatic and Van der Waals). The present study showed the development of the interlayer structure, basal spacing, and exfoliation energy in dependence on the ODAMIN content.