Silica aerogels have numerous properties which suggest applications such as ultra high efficiency thermal insulation. These properties relate directly to the aerogel's pore size distribution. The micro and meso pore size ranges can be investigated by normal small angle x-ray scattering and possibly, nitrogen adsorption. However, the measurement of larger pores (> 250 Å) is more difficult. Due to their limited mechanical strength, mercury porosimetry and nitrogen condensation can disrupt the gel structure and electron microscopy provides only limited large scale structure information. The use of small angle light scattering techniques seems to have promise, the only hurdle is that aerogels exhibit significant multiple scattering. This can be avoided if one observes the gels in the wet stage since the structure of the aerogel should be very similar to the wet gel (as the result of supercritical drying). Thus, if one can match the refractive index, the morphology can be probed. The combination of certain alcoholic solvents fit this index matching criteria. Preliminary results for the gel network (micron range) and primary particle structure (nanometer) are reported by using small angle light scattering and ultra-small angle x-ray scattering. The effects on structure over the length scale range of <1 nm to >5 μπι under different conditions (precursors, pH, etc.) are presented. The change in structure of an aerogel during isostatic compaction to 228 MPa (to simulate drying from wetting solvents) are also discussed.