VCu3(TeSe)2 is Sulvanite-derived structured and crystallizes in the orthorhombic Cmm2 space group. V(1) is bonded in a 4-coordinate geometry to two equivalent Cu(2), four equivalent Cu(1), two equivalent Te(1), and two equivalent Se(1) atoms. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a 6-coordinate geometry to two equivalent V(1), two equivalent Te(1), and two equivalent Se(1) atoms. In the second Cu site, Cu(2) is bonded in a 6-coordinate geometry to two equivalent V(1), two equivalent Te(1), and two equivalent Se(1) atoms. Te(1) is bonded to one V(1), one Cu(2), and two equivalent Cu(1) atoms to form TeVCu3 tetrahedra that share corners with two equivalent Te(1)VCu3 tetrahedra, corners with four equivalent Se(1)VCu3 tetrahedra,  an edgeedge with one Te(1)VCu3 tetrahedra, and edges with two equivalent Se(1)VCu3 tetrahedra. Se(1) is bonded to one V(1), one Cu(2), and two equivalent Cu(1) atoms to form distorted SeVCu3 tetrahedra that share corners with two equivalent Se(1)VCu3 tetrahedra, corners with four equivalent Te(1)VCu3 tetrahedra,  an edgeedge with one Se(1)VCu3 tetrahedra, and edges with two equivalent Te(1)VCu3 tetrahedra.
VCu3(TeSe)2 is Sulvanite-derived structured and crystallizes in the orthorhombic Cmm2 space group. V(1) is bonded in a 4-coordinate geometry to two equivalent Cu(2), four equivalent Cu(1), two equivalent Te(1), and two equivalent Se(1) atoms. There is one shorter (2.81 Å) and one longer (2.95 Å) V(1)-Cu(2) bond length. All V(1)-Cu(1) bond lengths are 2.89 Å. Both V(1)-Te(1) bond lengths are 2.57 Å. Both V(1)-Se(1) bond lengths are 2.37 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a 6-coordinate geometry to two equivalent V(1), two equivalent Te(1), and two equivalent Se(1) atoms. Both Cu(1)-Te(1) bond lengths are 2.57 Å. Both Cu(1)-Se(1) bond lengths are 2.41 Å. In the second Cu site, Cu(2) is bonded in a 6-coordinate geometry to two equivalent V(1), two equivalent Te(1), and two equivalent Se(1) atoms. Both Cu(2)-Te(1) bond lengths are 2.56 Å. Both Cu(2)-Se(1) bond lengths are 2.42 Å. Te(1) is bonded to one V(1), one Cu(2), and two equivalent Cu(1) atoms to form TeVCu3 tetrahedra that share corners with two equivalent Te(1)VCu3 tetrahedra, corners with four equivalent Se(1)VCu3 tetrahedra,  an edgeedge with one Te(1)VCu3 tetrahedra, and edges with two equivalent Se(1)VCu3 tetrahedra. Se(1) is bonded to one V(1), one Cu(2), and two equivalent Cu(1) atoms to form distorted SeVCu3 tetrahedra that share corners with two equivalent Se(1)VCu3 tetrahedra, corners with four equivalent Te(1)VCu3 tetrahedra,  an edgeedge with one Se(1)VCu3 tetrahedra, and edges with two equivalent Te(1)VCu3 tetrahedra.