ClO4-MgAl-LDH3, a MgAl (Mg/Al = 3) layered double hydroxide (LDH) containing perchlorate, swells and forms colloidal suspensions (sols) via the gel state in concentrated aqueous solutions of zwitterionic compounds related to amino acids. In total, 36 zwitterionic compounds with different molecular structures and additional functional groups were examined at various concentrations, and the sol-formation ability was judged by the transmittance (at lambda = 589 nm) of the resulting suspensions. At low concentration, the obtained suspensions were turbid, with transmittances of similar to 0% However, above the threshold concentration (0.3-1.0 M), osmotic swelling occurred and the transmittances of the suspensions increased sharply with increases in concentration to reach maximum values of 70-95%. The threshold concentration and maximum transmittance value depended on the structure and the location of the functional groups. The enhancement of the permittivity of water by the zwitterions and the formation of H-bond networks were assumed to be the reasons for the swelling phenomenon. Similar gel/sol formation was observed for ClO(4)(-)LDHs with Mg/Al = 2, Ni/Al = 2, 3, and Co/Al = 2 and some NO(3)(-)LDHs. Large ClO4-LDH films could be prepared by filtration of the colloidal suspensions followed by washing and drying processes.