Tb2Mo2O7 crystallizes in the cubic Fd-3m space group. Tb(1) is bonded in a body-centered cubic geometry to two equivalent O(1) and six equivalent O(2) atoms. Mo(1) is bonded to six equivalent O(2) atoms to form corner-sharing MoO6 octahedra. The corner-sharing octahedral tilt angles are 52°. There are two inequivalent O sites. In the first O site, O(1) is bonded to four equivalent Tb(1) atoms to form OTb4 tetrahedra that share corners with four equivalent O(1)Tb4 tetrahedra, corners with twelve equivalent O(2)Tb2Mo2 tetrahedra, and edges with six equivalent O(2)Tb2Mo2 tetrahedra. In the second O site, O(2) is bonded to two equivalent Tb(1) and two equivalent Mo(1) atoms to form distorted OTb2Mo2 tetrahedra that share corners with two equivalent O(1)Tb4 tetrahedra, corners with twelve equivalent O(2)Tb2Mo2 tetrahedra,  an edgeedge with one O(1)Tb4 tetrahedra, and edges with four equivalent O(2)Tb2Mo2 tetrahedra.
Tb2Mo2O7 crystallizes in the cubic Fd-3m space group. Tb(1) is bonded in a body-centered cubic geometry to two equivalent O(1) and six equivalent O(2) atoms. Both Tb(1)-O(1) bond lengths are 2.23 Å. All Tb(1)-O(2) bond lengths are 2.48 Å. Mo(1) is bonded to six equivalent O(2) atoms to form corner-sharing MoO6 octahedra. The corner-sharing octahedral tilt angles are 52°. All Mo(1)-O(2) bond lengths are 2.02 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to four equivalent Tb(1) atoms to form OTb4 tetrahedra that share corners with four equivalent O(1)Tb4 tetrahedra, corners with twelve equivalent O(2)Tb2Mo2 tetrahedra, and edges with six equivalent O(2)Tb2Mo2 tetrahedra. In the second O site, O(2) is bonded to two equivalent Tb(1) and two equivalent Mo(1) atoms to form distorted OTb2Mo2 tetrahedra that share corners with two equivalent O(1)Tb4 tetrahedra, corners with twelve equivalent O(2)Tb2Mo2 tetrahedra,  an edgeedge with one O(1)Tb4 tetrahedra, and edges with four equivalent O(2)Tb2Mo2 tetrahedra.