A comparative study to experimentally examine the effects of the guest molecular structure on the intercalated structure of a host layered material was systematically performed, aiming to control the structure of organosilicates. Layered octosilicate with hydrogen ions in the silicate interlayers (H-octosilicate) as the host was intercalated with water-insoluble guest alkylamines with different molecular structures, e.g., primary n-alkylamines with different alkyl chain lengths and secondary and tertiary dodecylamines with different numbers of dodecyl chains and methyl groups, in water by a simple method that we newly developed. The primary n-alkylamine-intercalated compounds had well-ordered structures with alkylamine bilayers in the interlayer space. The interlayer distances were relatively large compared with the quaternary ammonium ion-intercalated ones. Using the primary, secondary and tertiary dodecylamines, the structure of intercalated compounds drastically changed depending on the type of hydrocarbon group and the number of hydrogen atoms bonded to the nitrogen atom of the amine. The primary n-alkylamine-intercalated compounds showed good adsorption properties of methyl orange in water, which suggested that the intercalated compounds are promising candidates for removal of anionic dyes.