A new mixedsurfactants system using alkyl carboxylic acids and quaternized poly[bis(2-chloroethyl)ether-alt-1,3-bis[3-(dimethylamino)propyl] urea] (PEPU) as the co-template was used to synthesize mesoporoussilicamaterials with various morphologies and structures, including flakes, regular spheres, nanoparticles, and tube-spheres. The cationic polymer connected the anionic surfactant micelle to the anionic polysilicate species to induce the synthesis of the mesoporoussilicamaterials. The structure and property of the surfactant and the cationic polymer determined the formation of mesoporoussilica, and also had a signification influence on the morphology and structure of the final materials. To further explore the possible formation mechanism of these mesoporousmaterials, zeta potential was utilized to evaluate the interaction between the anionic surfactant and the cationic co-template. In addition, the structure, morphology, and porosity of these materials were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and N2 adsorption-desorption measurements.