Multimetallic clusters can be described as building blocks in intermetallics, compounds prepared from all metals and/or semi-metals, and in Zintl phases, a subset of intermetallics containing metals with large differences in electronegativity. In many cases, these intermetallic and Zintl phases provide the first clue for the possibilities of bond formation between metals and semi-metals. Recent advances in multimetallic clusters found in Zintl phases and nanoparticles focusing on Ge with transition metals and semi-metals is presented. Colloidal routes to Ge nanocrystals provide an opportunity for kinetically stabilized Ge-metal and Ge-semi-metal bonding. These routes provide crystalline nanoclusters of Ge, hereafter referred to as nanocrystals, that can be structurally characterized. Compositions of Ge nanocrystals containing transition metals, and the semi-metals, Sb, Bi, and Sn, whose structures have recently been elucidated through EXAFS, will be presented along with potential applications.