LiCuVO4 crystallizes in the orthorhombic Imma space group. Li(1) is bonded in a 6-coordinate geometry to two equivalent O(2) and four equivalent O(1) atoms. V(1) is bonded in a 6-coordinate geometry to two equivalent O(2) and four equivalent O(1) atoms. Cu(1) is bonded in a square co-planar geometry to four equivalent O(2) atoms. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1) and two equivalent V(1) atoms to form distorted OLi2V2 trigonal pyramids that share corners with four equivalent O(2)LiVCu2 trigonal pyramids, corners with seven equivalent O(1)Li2V2 trigonal pyramids,  an edgeedge with one O(1)Li2V2 trigonal pyramid, edges with two equivalent O(2)LiVCu2 trigonal pyramids, and  a faceface with one O(1)Li2V2 trigonal pyramid. In the second O site, O(2) is bonded to one Li(1), one V(1), and two equivalent Cu(1) atoms to form OLiVCu2 trigonal pyramids that share corners with four equivalent O(1)Li2V2 trigonal pyramids, corners with six equivalent O(2)LiVCu2 trigonal pyramids,  an edgeedge with one O(2)LiVCu2 trigonal pyramid, and edges with two equivalent O(1)Li2V2 trigonal pyramids.
LiCuVO4 crystallizes in the orthorhombic Imma space group. Li(1) is bonded in a 6-coordinate geometry to two equivalent O(2) and four equivalent O(1) atoms. Both Li(1)-O(2) bond lengths are 2.01 Å. All Li(1)-O(1) bond lengths are 2.29 Å. V(1) is bonded in a 6-coordinate geometry to two equivalent O(2) and four equivalent O(1) atoms. Both V(1)-O(2) bond lengths are 1.91 Å. There are two shorter (1.74 Å) and two longer (2.22 Å) V(1)-O(1) bond lengths. Cu(1) is bonded in a square co-planar geometry to four equivalent O(2) atoms. All Cu(1)-O(2) bond lengths are 1.93 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1) and two equivalent V(1) atoms to form distorted OLi2V2 trigonal pyramids that share corners with four equivalent O(2)LiVCu2 trigonal pyramids, corners with seven equivalent O(1)Li2V2 trigonal pyramids,  an edgeedge with one O(1)Li2V2 trigonal pyramid, edges with two equivalent O(2)LiVCu2 trigonal pyramids, and  a faceface with one O(1)Li2V2 trigonal pyramid. In the second O site, O(2) is bonded to one Li(1), one V(1), and two equivalent Cu(1) atoms to form OLiVCu2 trigonal pyramids that share corners with four equivalent O(1)Li2V2 trigonal pyramids, corners with six equivalent O(2)LiVCu2 trigonal pyramids,  an edgeedge with one O(2)LiVCu2 trigonal pyramid, and edges with two equivalent O(1)Li2V2 trigonal pyramids.