Highly ordered long-range lamellar silica was prepared using pure silicone surfactant as a structure-directing agent at neutral pH. Moreover, novel hierarchically mesostructured silica (designated ZSU-5) was templated from the mixture of silicone surfactant and TX-100 (C8Ph(EO)(10), Ph = phenyl) under neutral pH conditions. The results have demonstrated that the lamellar mesophase and the wormlike mesoporosity in the walls were separately templated from silicone surfactant and TX-100 in the mixed two different surfactant systems, and thus, hierarchically mesostructured silica was formed. We suggest that chain configuration of the surfactants is responsible for the formation of silica mesophase with different structures.