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LiUO3 is (Cubic) Perovskite structured and crystallizes in the cubic Pm-3m space group. The structure is three-dimensional and consists of one lithium molecule and one UO3 framework. In the UO3 framework, U5+ is bonded to six equivalent O2- atoms to form corner-sharing UO6 octahedra. The corner-sharing octahedral tilt angles are 0°. All U–O bond lengths are 2.14 Å. O2- is bonded in a linear geometry to two equivalent U5+ atoms.
LiUO3 is Calcite structured and crystallizes in the trigonal R3c space group. The structure is three-dimensional. Li1+ is bonded in a 3-coordinate geometry to six equivalent O2- atoms. There are three shorter (2.00 Å) and three longer (2.72 Å) Li–O bond lengths. U5+ is bonded to six equivalent O2- atoms to form corner-sharing UO6 octahedra. The corner-sharing octahedral tilt angles are 42°. There are three shorter (2.16 Å) and three longer (2.17 Å) U–O bond lengths. O2- is bonded in a 4-coordinate geometry to two equivalent Li1+ and two equivalent U5+ atoms.