Design of nanocatalysts for efficient heterogeneous catalytic systems is needed to high ingredients for environmental cleanup of organic pollutant species. Here, well-defined order NiO-silica monolithic catalysts with hexagonal P6mm and cubic Pm3n mesostructures were successfully fabricated by using an instant direct-templating method of lyotropic and microemulsion phases of Brij 76 (C18H37(OCH2CH2)(10)OH, C18EO10). Ordered hexagonal P6mm NiO/HOM-2 monoliths could be fabricated in lyotropic system of Brij 76 at phase composition domains of TMOS/Brij 76 (50 wt%). However, periodically ordered cubic Pm3n NiO-supported monoliths were synthesized in microemulsion system formed by addition of C-12-alkane to the hexagonal phase domains. This synthetic strategy also revealed that the NiO particles were well-dispersed into the silicate pore surface matrices of mesostructures. Monolithic NiO-silica composites with 2D hexagonal and 3D cubic geometries and with large particle morphologies show promise to act as catalysts. The current study revealed evidence of the advantages of nanoscale pore geometry and shape, and particle morphology of the supported silica monoliths in the design of nanocatalysts that can efficiently enhance the catalytic functionality in terms of stability, reversibility and reactivity. Furthermore, a key finding in our study was that 2D hexagonal and 3D cubic mesostructured NiO-silica catalysts retained the specific activity towards the oxidation reaction even after several regeneration/reuse cycles. Significant study of the mechanistic cyclization of the organic reactant using the density functional (DFT) calculations provided evidence of the key components of conformations of the functional model during the formation of the oxidation product. (C) 2007 Elsevier Inc. All rights reserved.