Nanoscale structure control by an intercalation method was reviewed. An open ring polymerization of ε-caprolaclam in interlayer spaces of layered clay mineral; montmorillonite, caused the indefinite swelling of silicate layers to form a nanoscale composit of 6-nylon and silicate layers of clay minerals. An interaction of guest molecules with the silicate surface arranged guest molecules and controlled the structure of intercalated compounds. We also found that aggregates of guest organic cations folded silica sheets of layered polysilicate, kanemite. Calcination of the complex of the folded silicate sheet and organic cations gave highly ordered mesoporous materials with a hexagonal array of uniform channels. An intercalation would be one of the effective methods to controll nanoscale structure of materials.