Mesoporous silica with large pores varying widely in size and with three-dimensional (3D) architectures are potential candidates for numerous applications.[1±5] Enlarging the pore size of mesoporous silica materials is an area that is actively researched. However, considerable attention has also been devoted to synthetic strategies for tailoring mesoporous silica dimensions in the 20±500 range through the use of various surfactant molecules, auxiliary chemicals, and synthetic conditions.[6±15] Furthermore, 3D mesoporous structures have been prepared through the phase transition of cylindrical phase assemblies by adding auxiliary molecules at ambient synthesis conditions. [7] The mesoporous silicates produced had an enlarged pore size; however, a loss of long-range order over the array was often observed, as revealed by the less well-resolved X-ray diffraction spectra and the broadening of the high-intensity peaks. In general, powdery mesoporous silica in micrometer-sized particles (1±2 lm) has been obtained; the formation of large, uniform monoliths was limited.[14±19]Furthermore, the utilization of a dilute surfactant in the synthesis of the mesoporous silica severely limited the ability to predict the mesophase topologies, because the primary phase of an amphiphile is affected by the interactions between the surfactant assemblies and the inorganic precursors.[5±7]Sol±gel synthesis of silica in a bulk lyotropic liquid-crystalline phase allows the inorganic precursors to precipitate in the synthesis solution during the solidification (i.e. rational precipitation), thereby allowing fabrication of large monoliths of the desired size and shape.[20±22] The use of a high template concentration (> 30 %) preserves the pre-existence of liquidcrystalline phases prior to solidification of the silica network, and thus allows a high degree of control over the amphiphilic phase domains and morphological organization of the mesopores. [21] However, even in these syntheses, the pore size is limited to a maximum of 40 by the type and composition of the amphiphiles.[20±23]Here, we developed a simple and versatile method that uses a lyotropic microemulsion of Brij 56 (C 16 EO 10 ) as a template for the synthesis of highly ordered silica monoliths (designated as HOM-n) with a large caged, cubic structure, a uniform pore size up to 80 , a high surface area (900 m 2 g ±1 ), and thick silicate walls of 100 . Furthermore, the long-range order of the structure was maintained. This direct templating method was successfully used here to fabricate well-defined, highly ordered 3D HOM-n monoliths of desired size and shape, such as spherical cubic Im3m (HOM-1), 3D hexagonal P6 3 /mmc (HOM-3), cubic Ia3d (HOM-5), cubic Pn3m (HOM-7), cubic Pm3n (HOM-9), novel cubic Fm3m (HOM-10), and cubic Pm3m (HOM-4). The phase transitions between the different cubic symmetries represent a significant feature during the synthesis of HOM-n monoliths in these microemulsion systems.Our microemulsion liquid-crystal phases were formed by mixing alkanes of various...