The crystal structure of the high-temperature modification of the compound Li2Zn5 was determined using single-crystal X-ray diffraction data. It is the first representative of a new binary structure type with triclinic space group P (1) over bar, where the parameters of the unit cell are a = 8.0073(3)angstrom, b = 11.5956(6)angstrom, c = 15.2956(5)angstrom, alpha = 96.39 degrees, beta = 101.92 degrees, and gamma = 108.13 degrees, the formula sum is Li11.748Zn31.113, Z = 2, and CCDC deposit number is 1861780. The title compound has a pseudohexagonal motif, made of 7- and 17-atom Li-zigzag chains and continuous Zn-chains, with the the relative placement of these large aggregates violating hexagonal symmetry. The structure may be decomposed into fragments, related to the AlB2 structure type, and could be obtained from multiplication of the unit cell, multiple substitution of Li atoms by triangles of Zn, insertion of Zn atoms, and deformation. Most structures of Li-Zn compounds, except LiZn, are highly symmetric but disordered. The possible causes of lower symmetry of beta-Li2Zn5 were analyzed using the results of DFT calculations. beta-Li2Zn5 shows high polarity of bonds, and Li atoms donate part of the electron density to Zn atoms.