LiV2O5 crystallizes in the orthorhombic Cmcm space group. Li(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. V(1) is bonded to one O(1), one O(2), and three equivalent O(3) atoms to form a mixture of distorted corner and edge-sharing VO5 trigonal bipyramids. There are three inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom. In the second O site, O(2) is bonded to two equivalent Li(1) and two equivalent V(1) atoms to form OLi2V2 tetrahedra that share corners with two equivalent O(2)Li2V2 tetrahedra, corners with two equivalent O(3)LiV3 trigonal pyramids, and edges with four equivalent O(3)LiV3 trigonal pyramids. In the third O site, O(3) is bonded to one Li(1) and three equivalent V(1) atoms to form distorted OLiV3 trigonal pyramids that share  a cornercorner with one O(2)Li2V2 tetrahedra, corners with three equivalent O(3)LiV3 trigonal pyramids, edges with two equivalent O(2)Li2V2 tetrahedra, and edges with two equivalent O(3)LiV3 trigonal pyramids.
LiV2O5 crystallizes in the orthorhombic Cmcm space group. Li(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. Both Li(1)-O(1) bond lengths are 2.02 Å. Both Li(1)-O(2) bond lengths are 2.17 Å. Both Li(1)-O(3) bond lengths are 2.49 Å. V(1) is bonded to one O(1), one O(2), and three equivalent O(3) atoms to form a mixture of distorted corner and edge-sharing VO5 trigonal bipyramids. The V(1)-O(1) bond length is 1.64 Å. The V(1)-O(2) bond length is 1.87 Å. There are two shorter (1.94 Å) and one longer (2.00 Å) V(1)-O(3) bond length. There are three inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom. In the second O site, O(2) is bonded to two equivalent Li(1) and two equivalent V(1) atoms to form OLi2V2 tetrahedra that share corners with two equivalent O(2)Li2V2 tetrahedra, corners with two equivalent O(3)LiV3 trigonal pyramids, and edges with four equivalent O(3)LiV3 trigonal pyramids. In the third O site, O(3) is bonded to one Li(1) and three equivalent V(1) atoms to form distorted OLiV3 trigonal pyramids that share  a cornercorner with one O(2)Li2V2 tetrahedra, corners with three equivalent O(3)LiV3 trigonal pyramids, edges with two equivalent O(2)Li2V2 tetrahedra, and edges with two equivalent O(3)LiV3 trigonal pyramids.