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Ag2O3 crystallizes in the cubic Pn-3m space group. The structure is three-dimensional. Ag3+ is bonded in a 6-coordinate geometry to six equivalent O2- atoms. All Ag–O bond lengths are 2.21 Å. O2- is bonded to four equivalent Ag3+ atoms to form a mixture of edge and corner-sharing OAg4 tetrahedra.
Ag2O3 crystallizes in the orthorhombic Fdd2 space group. The structure is three-dimensional. Ag3+ is bonded in a distorted square co-planar geometry to four O2- atoms. There are a spread of Ag–O bond distances ranging from 2.00–2.09 Å. There are two inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted trigonal non-coplanar geometry to three equivalent Ag3+ atoms. In the second O2- site, O2- is bonded in a water-like geometry to two equivalent Ag3+ atoms.