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CeBr3 crystallizes in the hexagonal P6_3/m space group. The structure is three-dimensional. Ce3+ is bonded in a 9-coordinate geometry to nine equivalent Br1- atoms. There are six shorter (3.06 Å) and three longer (3.25 Å) Ce–Br bond lengths. Br1- is bonded in a distorted trigonal non-coplanar geometry to three equivalent Ce3+ atoms.
Ce3Br is Uranium Silicide structured and crystallizes in the cubic Pm-3m space group. The structure is three-dimensional. Ce is bonded in a square co-planar geometry to four equivalent Br atoms. All Ce–Br bond lengths are 3.23 Å. Br is bonded to twelve equivalent Ce atoms to form a mixture of face and corner-sharing BrCe12 cuboctahedra.