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KAuO2 crystallizes in the orthorhombic Pmmm space group. The structure is three-dimensional. K1+ is bonded in a body-centered cubic geometry to eight equivalent O2- atoms. All K–O bond lengths are 2.91 Å. Au3+ is bonded in a square co-planar geometry to four equivalent O2- atoms. All Au–O bond lengths are 2.05 Å. O2- is bonded in a 6-coordinate geometry to four equivalent K1+ and two equivalent Au3+ atoms.
KAuO2 crystallizes in the orthorhombic Cmcm space group. The structure is three-dimensional. K1+ is bonded in a 6-coordinate geometry to six equivalent O2- atoms. There are two shorter (2.71 Å) and four longer (2.91 Å) K–O bond lengths. Au3+ is bonded in a rectangular see-saw-like geometry to four equivalent O2- atoms. All Au–O bond lengths are 2.04 Å. O2- is bonded to three equivalent K1+ and two equivalent Au3+ atoms to form a mixture of edge, face, and corner-sharing OK3Au2 trigonal bipyramids.