ThV2Al20 crystallizes in the cubic Fd-3m space group. Th(1) is bonded in a 16-coordinate geometry to four equivalent Al(1) and twelve equivalent Al(3) atoms. V(1) is bonded to six equivalent Al(2) and six equivalent Al(3) atoms to form VAl12 cuboctahedra that share corners with six equivalent V(1)Al12 cuboctahedra, edges with eighteen equivalent Al(3)ThAl10V cuboctahedra, and faces with six equivalent Al(3)ThAl10V cuboctahedra. There are three inequivalent Al sites. In the first Al site, Al(1) is bonded in a distorted linear geometry to two equivalent Th(1) and twelve equivalent Al(3) atoms. In the second Al site, Al(2) is bonded in a 12-coordinate geometry to two equivalent V(1), four equivalent Al(2), and six equivalent Al(3) atoms. In the third Al site, Al(3) is bonded to one Th(1), one V(1), two equivalent Al(1), three equivalent Al(2), and five equivalent Al(3) atoms to form distorted AlThAl10V cuboctahedra that share corners with fifteen equivalent Al(3)ThAl10V cuboctahedra, edges with two equivalent Al(3)ThAl10V cuboctahedra, edges with three equivalent V(1)Al12 cuboctahedra,  a faceface with one V(1)Al12 cuboctahedra, and faces with fifteen equivalent Al(3)ThAl10V cuboctahedra.
ThV2Al20 crystallizes in the cubic Fd-3m space group. Th(1) is bonded in a 16-coordinate geometry to four equivalent Al(1) and twelve equivalent Al(3) atoms. All Th(1)-Al(1) bond lengths are 3.13 Å. All Th(1)-Al(3) bond lengths are 3.21 Å. V(1) is bonded to six equivalent Al(2) and six equivalent Al(3) atoms to form VAl12 cuboctahedra that share corners with six equivalent V(1)Al12 cuboctahedra, edges with eighteen equivalent Al(3)ThAl10V cuboctahedra, and faces with six equivalent Al(3)ThAl10V cuboctahedra. All V(1)-Al(2) bond lengths are 2.56 Å. All V(1)-Al(3) bond lengths are 2.78 Å. There are three inequivalent Al sites. In the first Al site, Al(1) is bonded in a distorted linear geometry to two equivalent Th(1) and twelve equivalent Al(3) atoms. All Al(1)-Al(3) bond lengths are 3.09 Å. In the second Al site, Al(2) is bonded in a 12-coordinate geometry to two equivalent V(1), four equivalent Al(2), and six equivalent Al(3) atoms. All Al(2)-Al(2) bond lengths are 2.80 Å. There are two shorter (2.70 Å) and four longer (2.83 Å) Al(2)-Al(3) bond lengths. In the third Al site, Al(3) is bonded to one Th(1), one V(1), two equivalent Al(1), three equivalent Al(2), and five equivalent Al(3) atoms to form distorted AlThAl10V cuboctahedra that share corners with fifteen equivalent Al(3)ThAl10V cuboctahedra, edges with two equivalent Al(3)ThAl10V cuboctahedra, edges with three equivalent V(1)Al12 cuboctahedra,  a faceface with one V(1)Al12 cuboctahedra, and faces with fifteen equivalent Al(3)ThAl10V cuboctahedra. There are a spread of Al(3)-Al(3) bond distances ranging from 2.71-2.90 Å.