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LiAuAl2 crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two LiAuAl2 ribbons oriented in the (0, 1, 0) direction. Li is bonded in a linear geometry to two equivalent Al atoms. Both Li–Al bond lengths are 2.78 Å. Au is bonded in a linear geometry to two equivalent Al atoms. Both Au–Al bond lengths are 2.48 Å. Al is bonded in a linear geometry to one Li and one Au atom.
LiAuAl2 is Heusler structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Li is bonded in a distorted body-centered cubic geometry to six equivalent Au and eight equivalent Al atoms. All Li–Au bond lengths are 3.13 Å. All Li–Al bond lengths are 2.71 Å. Au is bonded in a distorted body-centered cubic geometry to six equivalent Li and eight equivalent Al atoms. All Au–Al bond lengths are 2.71 Å. Al is bonded in a body-centered cubic geometry to four equivalent Li and four equivalent Au atoms.