The intercalation behavior of dodecylamine into the interlayer of layered silicates was investigated in ethanol and n-hexane, using H-magadiite, H-kenyaite, and H-montmorillonite ion-exchanged with H(+) in a HCl solution. In ethanol, dodecylamine-magadiite and -kenyaite intercalates with well ordered basal spacing were obtained in 1.5 M and 1.2 M, respectively, whereas, in n-hexane, dodecylamine-magadiite and -kenyaite intercalates were formed with well ordered basal spacing at lower concentrations of 0.9 M and 0.5 M, respectively. This indicates that dodecylamine intercalates are formed well in n-hexane. In both solvents, the basal spacings of dodecylamine-magadiite and kenyaite intercalates, were ∼48 Å and ∼53 Å, respectively, thereby showing an abnormally large increase of ∼36 Å in their gallery height. In the dodecylamine-montmorillonite intercalates, the basal spacing were significantly increased from 26.2 Å to 41.4 Å between 0.9 M and 1.2 M, resulting in an increase of 15.4 Å and 26.0 Å in the gallery height. This implies that the intercalated dodecylamine molecules have quite different molecular configurations, such as an interlamellar bilayer that is parallel or perpendicular to the silicate sheet, dependent upon the amount of intercalated dodecylamine. In ethanol, the basal spacing of the dodecylamine-kenyaite intercalates were more ordered with a decreasing temperature, yet, in n-hexane, the spacing become more ordered with an increasing temperature.