K2LiVO4 crystallizes in the monoclinic C2/m space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 1-coordinate geometry to one O(3) atom. In the second K site, K(2) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(2), and four equivalent O(3) atoms. Li(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted LiO4 tetrahedra that share corners with four equivalent V(1)O4 tetrahedra and  an edgeedge with one Li(1)O4 tetrahedra. V(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form VO4 tetrahedra that share corners with four equivalent Li(1)O4 tetrahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one K(2), one Li(1), and one V(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to two equivalent K(2), two equivalent Li(1), and one V(1) atom. In the third O site, O(3) is bonded in a 6-coordinate geometry to one K(1), four equivalent K(2), and one V(1) atom.
K2LiVO4 crystallizes in the monoclinic C2/m space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 1-coordinate geometry to one O(3) atom. The K(1)-O(3) bond length is 2.67 Å. In the second K site, K(2) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(2), and four equivalent O(3) atoms. Both K(2)-O(1) bond lengths are 2.80 Å. Both K(2)-O(2) bond lengths are 3.23 Å. All K(2)-O(3) bond lengths are 2.92 Å. Li(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted LiO4 tetrahedra that share corners with four equivalent V(1)O4 tetrahedra and  an edgeedge with one Li(1)O4 tetrahedra. Both Li(1)-O(1) bond lengths are 1.98 Å. Both Li(1)-O(2) bond lengths are 2.01 Å. V(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form VO4 tetrahedra that share corners with four equivalent Li(1)O4 tetrahedra. The V(1)-O(2) bond length is 1.75 Å. The V(1)-O(3) bond length is 1.75 Å. Both V(1)-O(1) bond lengths are 1.75 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one K(2), one Li(1), and one V(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to two equivalent K(2), two equivalent Li(1), and one V(1) atom. In the third O site, O(3) is bonded in a 6-coordinate geometry to one K(1), four equivalent K(2), and one V(1) atom.