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CsGaO2 crystallizes in the cubic Fd-3m space group. The structure is three-dimensional. Cs1+ is bonded in a 12-coordinate geometry to twelve equivalent O2- atoms. All Cs–O bond lengths are 3.53 Å. Ga3+ is bonded to four equivalent O2- atoms to form corner-sharing GaO4 tetrahedra. All Ga–O bond lengths are 1.84 Å. O2- is bonded in a linear geometry to six equivalent Cs1+ and two equivalent Ga3+ atoms.
CsGaO2 crystallizes in the orthorhombic Pbca space group. The structure is three-dimensional. there are two inequivalent Cs1+ sites. In the first Cs1+ site, Cs1+ is bonded in a 8-coordinate geometry to eight O2- atoms. There are a spread of Cs–O bond distances ranging from 3.10–3.42 Å. In the second Cs1+ site, Cs1+ is bonded in a 4-coordinate geometry to eight O2- atoms. There are a spread of Cs–O bond distances ranging from 3.03–3.59 Å. There are two inequivalent Ga3+ sites. In the first Ga3+ site, Ga3+ is bonded to four O2- atoms to form corner-sharing GaO4 tetrahedra. All Ga–O bond lengths are 1.88 Å. In the second Ga3+ site, Ga3+ is bonded to four O2- atoms to form corner-sharing GaO4 tetrahedra. There are a spread of Ga–O bond distances ranging from 1.87–1.89 Å. There are four inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted bent 150 degrees geometry to four Cs1+ and two equivalent Ga3+ atoms. In the second O2- site, O2- is bonded in a distorted bent 150 degrees geometry to four Cs1+ and two equivalent Ga3+ atoms. In the third O2- site, O2- is bonded in a distorted bent 150 degrees geometry to four Cs1+ and two Ga3+ atoms. In the fourth O2- site, O2- is bonded in a distorted bent 150 degrees geometry to four Cs1+ and two Ga3+ atoms.