The 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, Pm1, 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.