This new synthetic method may also be extended to lithium-containing Zintl phases (LiH is commercially available) as well as to alkali metal-tetrel Zintl compounds of other compositions, e.g. This method provides large quantities of high quality Na 4Si 4 and Na 4Ge 4 without the need for specialized laboratory equipment, such as Schlenk lines, niobium/tantalum containers, or an arc welder, thereby expanding the accessibility and chemical utility of these phases by making them more convenient to prepare. TG/DSC analysis of the reaction of NaH and Ge indicates that ball milling reduces the temperature for reaction and confirms the formation temperature. Moderate ball-milling and excess NaH or KH facilitate the formation of pure Na 4Si 4, Na 4Ge 4 or K 4Ge 4 at 420 ☌ (Na 4Si 4) or 270 ☌ (both M 4Ge 4 compounds, M = Na, K). The influence of specific reaction conditions on the purity of these Zintl phases has been studied by controlling five factors: the method of reagent mixing (manual or ball milled), the stoichiometry between raw materials, the reaction temperature, the heating time and the gas flow rate. The method was also applied to K 4Ge 4, using KH and Ge as raw materials, to show the versatility of this approach. In this study, a simple scalable route has been applied to prepare Zintl phases of composition Na 4Si 4 and Na 4Ge 4 using the reaction between NaH and Si or Ge at low temperature (420 ☌ for Na 4Si 4 and 270 ☌ for Na 4Ge 4). The monoclinic Zintl phases, Na 4Si 4 and Na 4Ge 4, contain isolated homo-tetrahedranide 4− and 4− clusters surrounded by alkali metal cations. Na 4Si 4 and Na 4Ge 4 are ideal chemical precursors for inorganic clathrate structures, clusters, and nanocrystals.