CsScO2 is Cuprite-derived structured and 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 3.77 Å. Sc3+ is bonded to four equivalent O2- atoms to form corner-sharing ScO4 tetrahedra. All Sc–O bond lengths are 1.97 Å. O2- is bonded in a linear geometry to six equivalent Cs1+ and two equivalent Sc3+ atoms.