The stannides LiAuSn and LiAu₃Sn₄ were synthesized from the elements by reaction in sealed tantalum tubes in a resistance furnace. LiAuSn crystallizes with a ZrBeSi type structure, space group P6₃/mmc: a = 467.08(8) pm, c = 603.7(1) pm, wR2 = 0.0403, 87 F² values, 7 variables. The gold and tin atoms form a planar network of condensed Au₃Sn₃ hexagons (270 pm Au–Sn) which are rotated by 60° around the c axis in every other layer. The lithium atoms are located between these layers. LiAuSn may be classified as a lithium intercalated heterographite according to Li⁺[AuSn]⁻. LiAu₃Sn₄ adopts a polar structure, space group P6₃mc, which has been refined for an inversion twin: a = 448.31(6) pm, c = 2055.7(4) pm, wR2 = 0.0814, BASF = 0.13(2), 699 F² values, 25 variables. This new structure type may be considered as an intergrowth of slightly distorted NiAs and CaAl₂Si₂ related slabs of compositions AuSn and LiAu₂Sn₂. Short (285 pm) Au–Au distances within the AuSn slab are indicative for significant Au–Au bonding. The lithium atoms fill tetrahedral voids formed by the gold atoms within the LiAu₂Sn₂ slab. Chemical bonding analysis by TB-LMTO-ASA calculations confirm the covalently bonded [AuSn]⁻ polyanion in LiAuSn. Each network atom participates in three two-electron two-center Au–Sn σ-bonds, whereas π-bonding is absent. The crystal orbital Hamilton populations (COHP) analysis of LiAu₃Sn₄ reveals almost equal Au–Sn bonding energies for the three Au atoms despite their different tin environments. Au–Au bonding in LiAu₃Sn₄ is strong and shows the same electronic features as in binary AuSn with NiAs structure.