AbstractThe synthesis, structural characterization, and chemical bonding peculiarities of three new binary Li–In intermetallides are reported. The crystal structures of these compounds were determined by single‐crystal X‐ray diffraction analysis. The compositions obtained after structure refinements were Li22–xIn8+x (x = 0.1) [new structure type, monoclinic crystal system, Pearson symbol mS30, space group C2/m, a = 14.156(3), b = 4.729(1), c = 8.617(2) Å, β = 105.89(1)°, R1 = 0.0279, wR2 = 0.0583 for 669 reflections], Li11–xIn4+x (x = 1.05) [new structure type, trigonal, P$\bar {3}$m1, hP15, a = 4.7480(7), c = 14.283(3) Å, R1 = 0.0323, wR2 = 0.0741 for 277 reflections], and Li10–xIn2+x (x = 1.59) [new structure type, hexagonal, P6/mmm, hP12, a = 4.6975(7), c = 11.526(2) Å, R1 = 0.0680, wR2 = 0.1358 for 127 reflections]. The Li22–xIn8+x (x = 0.1) structure is related to the structure of lithium (W‐type). The structure of Li11–xIn4+x (x = 1.05) can be described as a derivative of the CdI2 type. Li10–xIn2+x (x = 1.59) can be derived from the Li2Pt structure. [In2@Li20] clusters composed of 20 lithium atoms, which surround a In–In pair, are detected in the structure of all three investigated compounds. TB‐LMTO (Tight‐Binding Linear Muffin‐Tin Orbital) calculations indicate strong covalent In–In interactions and the presence of [In2@Li20] clusters in these new binary indides.