The oriented attachment of inorganic nanocrystals controlled by adsorbed surfactants can lead to the formation of hollow nanoarchitectures with various well-defined morphologies. In this paper, Mg(OH)(2) hollow nanospheres and the "encapsulated" catanionic vesicles could be simultaneously constructed by using the cationic surfactant of cetyltrimethylammonium hydroxide (CTAOH) and the anionic surfactant of magnesium dodecyl sulfate (Mg(DS)(2)) as reactants at pH 11.0. Therein, the driven forces for the oriented attachment of Mg(OH)(2) particles should involve hydrophobic interactions among pendent surfactants. Similarly, the secondary architectures derived from catanionic surfactant-Mg(OH)(2) hollow nanospheres could also be encountered under nonequilibrium conditions. Interestingly, the coating of Mg(OH)(2) particles facilitated the direct observation of nanosized surfactant self-assemblies and the membrane fusion without using general staining methods. After the crystalline fusion of coating particles, Mg(OH)(2) hollow nanospheres and the correspondingly shell-used Superstructures were obtained, implying a simple and versatile method for the study of lipid membranes and the fabrication of M(OH)(2) (M = divalent metal ions) hollow architectures.