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LiCa2Pb crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two LiCa2Pb ribbons oriented in the (1, 0, 0) direction. Li is bonded in a linear geometry to two equivalent Ca atoms. Both Li–Ca bond lengths are 3.39 Å. Ca is bonded in a distorted linear geometry to one Li and one Pb atom. The Ca–Pb bond length is 3.13 Å. Pb is bonded in a linear geometry to two equivalent Ca atoms.
LiCa2Pb is Heusler structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Li is bonded in a body-centered cubic geometry to eight equivalent Ca atoms. All Li–Ca bond lengths are 3.34 Å. Ca is bonded to four equivalent Li and four equivalent Pb atoms to form a mixture of distorted edge, face, and corner-sharing CaLi4Pb4 tetrahedra. All Ca–Pb bond lengths are 3.34 Å. Pb is bonded in a body-centered cubic geometry to eight equivalent Ca atoms.