PbBi12O20 crystallizes in the cubic I23 space group. Pb(1) is bonded to four equivalent O(2) atoms to form PbO4 tetrahedra that share corners with twelve equivalent Bi(1)O5 square pyramids. Bi(1) is bonded to one O(2), one O(3), and three equivalent O(1) atoms to form distorted BiO5 square pyramids that share corners with eight equivalent Bi(1)O5 square pyramids,  a cornercorner with one Pb(1)O4 tetrahedra, and  an edgeedge with one Bi(1)O5 square pyramid. There are three inequivalent O sites. In the first O site, O(3) is bonded in a trigonal planar geometry to three equivalent Bi(1) atoms. In the second O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to three equivalent Bi(1) atoms. In the third O site, O(2) is bonded to one Pb(1) and three equivalent Bi(1) atoms to form corner-sharing OBi3Pb tetrahedra.
PbBi12O20 crystallizes in the cubic I23 space group. Pb(1) is bonded to four equivalent O(2) atoms to form PbO4 tetrahedra that share corners with twelve equivalent Bi(1)O5 square pyramids. All Pb(1)-O(2) bond lengths are 2.08 Å. Bi(1) is bonded to one O(2), one O(3), and three equivalent O(1) atoms to form distorted BiO5 square pyramids that share corners with eight equivalent Bi(1)O5 square pyramids,  a cornercorner with one Pb(1)O4 tetrahedra, and  an edgeedge with one Bi(1)O5 square pyramid. The Bi(1)-O(2) bond length is 2.56 Å. The Bi(1)-O(3) bond length is 2.25 Å. There are a spread of Bi(1)-O(1) bond distances ranging from 2.09-2.56 Å. There are three inequivalent O sites. In the first O site, O(3) is bonded in a trigonal planar geometry to three equivalent Bi(1) atoms. In the second O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to three equivalent Bi(1) atoms. In the third O site, O(2) is bonded to one Pb(1) and three equivalent Bi(1) atoms to form corner-sharing OBi3Pb tetrahedra.