Cs2GeTe4 crystallizes in the orthorhombic Pnma space group. Cs(1) is bonded in a 9-coordinate geometry to two equivalent Te(1), three equivalent Te(3), and four equivalent Te(2) atoms. Ge(1) is bonded to one Te(1), one Te(3), and two equivalent Te(2) atoms to form GeTe4 tetrahedra that share corners with two equivalent Te(2)Cs4GeTe pentagonal pyramids. There are three inequivalent Te sites. In the first Te site, Te(1) is bonded in a distorted pentagonal planar geometry to four equivalent Cs(1) and one Ge(1) atom. In the second Te site, Te(2) is bonded to four equivalent Cs(1), one Ge(1), and one Te(2) atom to form distorted TeCs4GeTe pentagonal pyramids that share corners with five equivalent Te(2)Cs4GeTe pentagonal pyramids,  a cornercorner with one Ge(1)Te4 tetrahedra, and edges with four equivalent Te(2)Cs4GeTe pentagonal pyramids. In the third Te site, Te(3) is bonded in a 7-coordinate geometry to six equivalent Cs(1) and one Ge(1) atom.
Cs2GeTe4 crystallizes in the orthorhombic Pnma space group. Cs(1) is bonded in a 9-coordinate geometry to two equivalent Te(1), three equivalent Te(3), and four equivalent Te(2) atoms. There is one shorter (3.88 Å) and one longer (3.90 Å) Cs(1)-Te(1) bond length. There are a spread of Cs(1)-Te(3) bond distances ranging from 4.13-4.21 Å. There are a spread of Cs(1)-Te(2) bond distances ranging from 3.93-4.13 Å. Ge(1) is bonded to one Te(1), one Te(3), and two equivalent Te(2) atoms to form GeTe4 tetrahedra that share corners with two equivalent Te(2)Cs4GeTe pentagonal pyramids. The Ge(1)-Te(1) bond length is 2.58 Å. The Ge(1)-Te(3) bond length is 2.56 Å. Both Ge(1)-Te(2) bond lengths are 2.68 Å. There are three inequivalent Te sites. In the first Te site, Te(1) is bonded in a distorted pentagonal planar geometry to four equivalent Cs(1) and one Ge(1) atom. In the second Te site, Te(2) is bonded to four equivalent Cs(1), one Ge(1), and one Te(2) atom to form distorted TeCs4GeTe pentagonal pyramids that share corners with five equivalent Te(2)Cs4GeTe pentagonal pyramids,  a cornercorner with one Ge(1)Te4 tetrahedra, and edges with four equivalent Te(2)Cs4GeTe pentagonal pyramids. The Te(2)-Te(2) bond length is 2.81 Å. In the third Te site, Te(3) is bonded in a 7-coordinate geometry to six equivalent Cs(1) and one Ge(1) atom.