Various siliceous nanostructures have been successfully synthesized through the co-organization of organic molecules and inorganic silica source under mild pH conditions (pH approximately 5). A biodegradable block copolymer P123 [EO20PO70EO20, EO is poly (ethylene oxide), PO is poly (propylene oxide)] is employed as a marcomolecular template and Na2SiO39H2O as a silica source. By changing the concentrations of the reactants and/or reaction temperature, siliceous multilamellar vesicles, unilamellar nano-foams and multilamellar vesicles with sponge-like walls have been obtained. Our work provides a convenient and bioinspired route to obtain siliceous nanostructured materials with adjustable and multi-level pore structures as well as rich morphologies, which is important to understand the biomineralization mechanism. Such artificial silica nanoporous materials may find potential applications in catalysis, separations, electronics, and photonics, etc.