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RbO3I crystallizes in the trigonal R3m space group. The structure is three-dimensional. Rb1+ is bonded in a 12-coordinate geometry to twelve equivalent O2- atoms. There are a spread of Rb–O bond distances ranging from 3.12–3.56 Å. O2- is bonded in a distorted single-bond geometry to four equivalent Rb1+ and one I5+ atom. The O–I bond length is 1.84 Å. I5+ is bonded in a 6-coordinate geometry to three equivalent O2- atoms.
RbO3I crystallizes in the monoclinic Cm space group. The structure is two-dimensional and consists of one RbO3I sheet oriented in the (0, 0, 1) direction. Rb1+ is bonded in a distorted rectangular see-saw-like geometry to four equivalent O2- atoms. There are two shorter (3.00 Å) and two longer (3.12 Å) Rb–O bond lengths. There are two inequivalent O2- sites. In the first O2- site, O2- is bonded in a water-like geometry to two equivalent O2- atoms. Both O–O bond lengths are 1.32 Å. In the second O2- site, O2- is bonded in a 3-coordinate geometry to two equivalent Rb1+, one O2-, and one I5+ atom. The O–I bond length is 3.04 Å. I5+ is bonded in a 4-coordinate geometry to two equivalent O2- atoms.