A biomimetic templating approach to the synthesis of lamellar silicas is demonstrated. The procedure is based on the hydrolysis and cross-linking of a neutral silicon alkoxide precursor in the interlayered regions of multilamellar vesicles formed from a neutral diamine bola-amphiphile. Unlike earlier surfactant-templating approaches, this method produces porous lamellar silicas (designated MSU-V) with vesicular particle morphology, exceptional thermal stability, a high degree of framework cross-linking, unusually high specific surface area and pore volume, and sorption properties that are typical of pillared lamellar materials. This approach circumvents the need for a separate pillaring step in building porosity into a lamellar host structure and offers new opportunities for the direct fabrication of adsorbents, catalysts, and nanoscale devices.