jats:titleAbstract</jats:title>jats:pThe novel ternary Zintl phase Lijats:sub3</jats:sub>NaGejats:sub2</jats:sub> comprises alkali‐metal cations and [Gejats:sub2</jats:sub>]jats:sup4−</jats:sup> dumbbells. The diatomic [Gejats:sub2</jats:sub>]jats:sup4−</jats:sup> unit is characterized by the shortest Ge−Ge distance (2.390(1) Å) ever observed in a Zintl phase and thus represents the first Ge=Ge double bond under such conditions, as also suggested by the (8−jats:italicN</jats:italic>) rule. Raman measurements support these findings. The multiple‐bond character is confirmed by electronic‐structure calculations, and an upfield jats:sup6</jats:sup>Li NMR shift of −10.0 ppm, which was assigned to the Li cations surrounded by the π systems of three Ge dumbbells, further underlines this interpretation. For the unperturbed, ligand‐free dumbbell in Lijats:sub3</jats:sub>NaGejats:sub2</jats:sub>, the π‐ bonding pjats:subjats:italicy</jats:italic></jats:sub> and pjats:subjats:italicz</jats:italic></jats:sub> orbitals are degenerate as in molecular oxygen, which has singly occupied orbitals. The partially filled π‐type bands of the neat solid Lijats:sub3</jats:sub>NaGejats:sub2</jats:sub> cross the Fermi level, resulting in metallic properties. Lijats:sub3</jats:sub>NaGejats:sub2</jats:sub> was synthesized from the elements as well as from binary reactants and subsequently characterized crystallographically.</jats:p>