The chemistry and physics of small clusters of atoms (1-100 nm) has received considerable attention in recent years because these assemblies often have properties between the molecular and bulk solid-state limits. The different properties can be explained in terms of the large fraction of atoms that are at the surface of a cluster as compared to the interior. Although the synthesis and properties of metal and semiconductor clusters, metallocarbohedrenes, fullerenes, and nanotubes are the subject of extensive investigations, little attention has been paid to cluster-assembled porous materials. This oversight is of particular interest to us since we believe that aerogels are one of the few monolithic materials presently available where the benefits of cluster assembly can be demonstrated. In particular, the unique optical, thermal, acoustic, mechanical, and electrical properties of aerogels are directly related to their nanostructure, which is composed of interconnected particles (3-30 nrm) with small interstitial pores (< 50 nm). This structure leads to extremely high surface areas (400-1100 m2/g) with a large fraction of the atoms covering the surface of the interconnected particles. As a result of these structural features, carbon aerogels are finding applications as electrodes in supercapacitors with high energy and power densities.