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RbKAu2 crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two RbKAu2 ribbons oriented in the (1, 0, 0) direction. Rb1+ is bonded in a linear geometry to two equivalent Au1- atoms. Both Rb–Au bond lengths are 3.22 Å. K1+ is bonded in a linear geometry to two equivalent Au1- atoms. Both K–Au bond lengths are 3.08 Å. Au1- is bonded in a linear geometry to one Rb1+ and one K1+ atom.
RbKAu2 is Heusler structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Rb1+ is bonded in a body-centered cubic geometry to eight equivalent Au1- atoms. All Rb–Au bond lengths are 3.56 Å. K1+ is bonded in a body-centered cubic geometry to eight equivalent Au1- atoms. All K–Au bond lengths are 3.56 Å. Au1- is bonded in a body-centered cubic geometry to four equivalent Rb1+ and four equivalent K1+ atoms.