Structure organization of the cubic silicate species, Si8O208-(Si-8), by the cationic surfactant, CH3(CH2)(15)N(CH3)(3)(+), leads to mesophasic precipitates with layer or rod-based structures depending on the conditions of the precipitation. Further ordering of the structures of these precipitates has been achieved by acidic vapor treatment leading to ordered materials with cubic (MCM-48), lamellar, and hexagonal (MCM-41) mesostructures. For the first time, step-by-step structural transformations have been observed, which follow the-sequence given here, during vapor phase treatment : layered precipitate (L(0)) --> cubic (V-1) --> lamellar (L(1)) --> hexagonal (H-1). These results strongly support a mechanism in which, under typical synthetic conditions, silicates and surfactants mutually organize into mesoscopic assemblies with geometries close to those of discs, rods,or spheres as determined by charge density matching and then these assemblies further condense into ordered lamellar, hexagonal, or cubic structures depending on the final reaction conditions. The present results also demonstrate that it is possible to achieve structure-tailoring and better framework ordering of these mesostructural materials.