While the sol-gel polymerizations of tetraalkoxy- and organotrialkoxysilanes have been extensively studied, there have been few reports of similar investigations with the analogous tetraalkoxygermanium and organotrialkoxygermanium compounds. Germanium alkoxides have received less attention due, in part to their higher cost, but also their greater reactivity towards hydrolysis and condensation reactions. Germanium oxide materials are potentially interesting because the Ge-O-Ge linkage is labile (compared with the siloxane bond in silica gels and polysilsesquioxanes) opening up the possibility of further chemical modification of the polymeric architecture. This may permit hydrolytic reorganization of germanium oxide networks under relatively mild conditions. In this paper, we will present the results of our investigations of the solgel polymerizations of tetraethoxygermanium 1, tetraisopropoxygermanium 2, and methyltriethoxy-germanium 3 to afford network materials as both xerogels and aerogels.