Lithium cations sit in the center of the oxygen "windows" defined by the vertex-sharing TiO(6) octahedra of the title compound (see picture), as shown from neutron diffraction data. The octahedra are tilted to optimize the bond distances between the atoms. The unusual coordination and the partially unoccupied sublattice (occupancy factors 1/6 and (1/2) for Li and La, respectively) account for the high mobility of the Li(+) cations.