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Abstract A new ternary lithium zinc germanide, Li_13.83Zn_1.17(2)Ge₄, was synthesized by a high‐temperature solid state reaction of the respective elements. The crystal structure was determined by single‐crystal X‐ray diffraction methods. The new phase crystallizes in the body‐centered cubic space groupI3d(no. 220) with unit cell parameter of 10.695(1) Å. The crystal structure refinements show that the parent Li₁₅Ge₄structure is stabilized as Li_15−xZn_xGe₄(x≈1) via random substitution of Li atoms by the one‐electron‐richer atoms of the element Zn, by virtue of which the number of valence electrons increases, leading to a more electronically stable system. The substitution effects in the parent Li₁₅Ge₄structure were investigated through both theory and experiment, which confirm that the Zn atoms in this structure prefer to occupy only one of the two available crystallographic sites for Li. The preferred substitution pattern established from experimental results is supported by DFT electronic structure calculations, which also explore the subtleties of the chemical bonding and the electronic properties of the title compounds.