Nanoporous materials are potentially useful for their permeation, dielectric, thermal and optical properties. One of the major impacts of these materials in the future could be in replacing the existing thermal insulation technology based on macroporous (~ 40-100 µm) structures that require harmful blowing agents or high vacuum conditions (< 1 mbar) to attain thermal conductivity lower than that of air (24-26 mW/m∙K at ambient conditions). Highly nanoporous materials (pore size ~ 100-150 nm and porosity ≥ 85 %) that take advantage of the Knudsen effect and low solids contribution to heat conduction are therefore required. The potential for designing such materials by carrying out templated cross-linking reactions in microemulsion and colloids and non-templated reactions in organic and aqueous solvents (sol-gel technique) were investigated. It was found that the templates in these techniques helped in imposing some fine pore structures (< 200 nm) characteristic of them but the coarser pores (> 1 µm) that are formed due to phase separation and aggregation effects upon cross-linking could not be avoided. As a result the thermal performances of these materials were in between the conventional macroporous foam (~ 40-100 µm) and nanoporous material (~ 150 nm) based on sol-gel.