A Mg2+-induced vesicle phase was prepared from a mixture of tetradecyldimethylamine oxide (C14DMAO) and magnesium dodecyl sulfate [Mg(DS)2] in aqueous solution. Study of the phase behavior shows that at the appropriate mixing ratios, Mg2+-ligand coordination between C14DMAO and Mg(DS)2 results in the formation of molecular bilayers, in which Mg2+ can firmly bind to the head groups of the two surfactants. The area of the head group can be reduced because of the complexation. In this case, no counterions exist in aqueous solution because of the fixation of Mg2+ ions to the bilayer membranes. Therefore, the charges of the bilayer membranes are not shielded by salts. The birefringent solutions of Mg(DS)2 and C14DMAO mixtures consist of vesicles which were determined by transmission electron microscopy (TEM) images and rheological measurements. Magnesium oxide (MgO) nanoplates were obtained via the decomposition of Mg(OH)2 which were synthesized in Mg2+-induced vesicle phase which was used as the microreactor under the existence of ammonia hydroxide. The morphologies and structures of the obtained MgO nanoplates have been characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results indicate that the crystal growth is along the (111) direction which can be affected by the presence of a vesicle phase having a fixation of Mg2+ ions to the bilayer membranes.