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RbO2 crystallizes in the tetragonal I4/mmm space group. The structure is three-dimensional. Rb is bonded in a distorted q4 geometry to ten equivalent O atoms. There are two shorter (2.85 Å) and eight longer (3.04 Å) Rb–O bond lengths. O is bonded in a 6-coordinate geometry to five equivalent Rb and one O atom. The O–O bond length is 1.35 Å.
RbO2 is Anatase structured and crystallizes in the tetragonal I4_1/amd space group. The structure is three-dimensional. Rb is bonded to six equivalent O atoms to form a mixture of corner and edge-sharing RbO6 octahedra. The corner-sharing octahedral tilt angles are 11°. There are four shorter (2.79 Å) and two longer (3.04 Å) Rb–O bond lengths. O is bonded in a T-shaped geometry to three equivalent Rb atoms.
RbO2 crystallizes in the tetragonal P4/mmm space group. The structure is three-dimensional. Rb is bonded to six O atoms to form a mixture of edge and corner-sharing RbO6 octahedra. The corner-sharing octahedral tilt angles are 0°. There are four shorter (2.90 Å) and two longer (2.99 Å) Rb–O bond lengths. There are two inequivalent O sites. In the first O site, O is bonded in a linear geometry to two equivalent Rb atoms. In the second O site, O is bonded in a square co-planar geometry to four equivalent Rb atoms.