A series of bis-cationic bolaamphiphiles was synthesized containing N-methylimidazolium head-groups, separated by alkyl chains of 12, 16 and 24 methylene units. Their critical micelle concentrations were determined, with subsequent flooding experiments revealing the tendency for the formation of hexagonal mesophases at high surfactant concentrations. The surfactants were employed as templates for silica formation, at ca. four times their critical micelle concentrations: permitting porous, nanoparticulate silicas to be prepared. Analysis of the materials by small angle X-ray diffraction indicated that, in the case of the template possessing 24 methylene units, the silica obtained exhibited a 2 D hexagonal pore arrangement. Silica surface areas ranged from 500 to 1000 m² g^-1, and pore diameters from 10 to 22 Å. Hence manipulation of surfactant chain length permits direct access to supermicroporous materials: with pore diameters between the mesopore and micropore ranges, small enough to have an influence on reaction selectivity, and otherwise difficult to obtain. Herein we report on the inherent catalytic behavior of these materials and their performance when used as supports for metal nanoparticles.