Li2TiV3O8 is Spinel-derived structured and crystallizes in the trigonal R-3m space group. Li(1) is bonded to one O(1) and three equivalent O(2) atoms to form LiO4 tetrahedra that share corners with three equivalent Ti(1)O6 octahedra and corners with nine equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-59°. Ti(1) is bonded to six equivalent O(2) atoms to form TiO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra and edges with six equivalent V(1)O6 octahedra. V(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form VO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1) and three equivalent V(1) atoms to form distorted OLiV3 trigonal pyramids that share corners with three equivalent O(1)LiV3 trigonal pyramids, corners with nine equivalent O(2)LiTiV2 trigonal pyramids, and edges with three equivalent O(2)LiTiV2 trigonal pyramids. In the second O site, O(2) is bonded to one Li(1), one Ti(1), and two equivalent V(1) atoms to form distorted OLiTiV2 trigonal pyramids that share corners with three equivalent O(1)LiV3 trigonal pyramids, corners with nine equivalent O(2)LiTiV2 trigonal pyramids,  an edgeedge with one O(1)LiV3 trigonal pyramid, and edges with two equivalent O(2)LiTiV2 trigonal pyramids.
Li2TiV3O8 is Spinel-derived structured and crystallizes in the trigonal R-3m space group. Li(1) is bonded to one O(1) and three equivalent O(2) atoms to form LiO4 tetrahedra that share corners with three equivalent Ti(1)O6 octahedra and corners with nine equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-59°. The Li(1)-O(1) bond length is 1.98 Å. All Li(1)-O(2) bond lengths are 2.02 Å. Ti(1) is bonded to six equivalent O(2) atoms to form TiO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra and edges with six equivalent V(1)O6 octahedra. All Ti(1)-O(2) bond lengths are 1.99 Å. V(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form VO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. Both V(1)-O(1) bond lengths are 2.02 Å. All V(1)-O(2) bond lengths are 2.03 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1) and three equivalent V(1) atoms to form distorted OLiV3 trigonal pyramids that share corners with three equivalent O(1)LiV3 trigonal pyramids, corners with nine equivalent O(2)LiTiV2 trigonal pyramids, and edges with three equivalent O(2)LiTiV2 trigonal pyramids. In the second O site, O(2) is bonded to one Li(1), one Ti(1), and two equivalent V(1) atoms to form distorted OLiTiV2 trigonal pyramids that share corners with three equivalent O(1)LiV3 trigonal pyramids, corners with nine equivalent O(2)LiTiV2 trigonal pyramids,  an edgeedge with one O(1)LiV3 trigonal pyramid, and edges with two equivalent O(2)LiTiV2 trigonal pyramids.