Since the discovery of mesoporous silica molecular sieves by Beck et al. (Beck et al., 1992; Kresge et al., 1992), mesoporous materials have opened many new possibilities for application in the fields of catalysis (Tanev et al., 1994), separation, and nanoscience (Wu & Bein, 1994; Agger et al., 1998; Li et al., 2003; Yu et al., 2005]. In recent years, fabrication of silica materials with designed structure (e.g. thin films, monoliths, hexagonal prisms, toroids, discoids, spirals, dodecahedron and hollow sphere shapes) is an important research in modern materials chemistry. Among them the fabrication of monodispersed hollow spheres with control size and shape is fastest developing area (Schacht et al., 1996; Bruinsma et al., 1997; Fowler et al., 2001). It is generally accepted that hollow sphere with mesopores will exhibit more advantages in mass diffusion and transportation as compared with conventional hollow spheres with solid shell. They can serve as a small container for application in catalysis and control release studies (Mathlowitz et al., 1997; Huang & Remsen, 1999). The methods currently used to fabricate a wide range of stable hollow spheres include nozzle reactor processes, emulsion/phase separation, sol-gel processing, and sacrificial core techniques. The fabrication of hollow spheres has been greatly impacted by the layer-by-layer (LbL) self-assembly technique (Decher, 1997). This method allows the construction of composite multilayer assemblies based on the electrostatic attraction between nanoparticles and oppositely charged polyions. By varying the synthetic methodology and reactants, it is highly probable to achieve the materials with interesting morphology and properties.