A novel bioinspired approach for ordered mesoporous silica was developed on the basis of the synergic coassembly between polyamine and an anionic surfactant as a template. With the help of cationic polyamine, anionic surfactant micelles could be utilized as a mesostructure template, whereas with the aid of the anionic surfactant micelles the cationic polyamine chains underwent aggregation to exert their ability to induce silica condensation. Mesoporous silicas with well-ordered mesostructure of Fd-3m symmetry and 3D hexagonal close-packed mesostructure (hcp) were fabricated. Because of the abundant types of anionic surfactants and polyamines, the synthesis approach can be regarded as a general method for anionic-surfactant-templated mesoporous silica, and new mesostructures and morphologies are expected.