Three representative oxides of the La2/3-xLi3xTiO3 system have been studied by selected area electron diffraction (SAED), high-resolution transmission electron microscopy (HRTEM), and powder synchrotron X-ray diffraction. HRTEM showed that the materials have a complex microstructure. The SAED and HRTEM results have allowed us to propose a model to refine the crystal structure of these oxides that also accounts for their microstructure. The materials have a perovskite-related structure with a diagonal unit cell (root2a(p) x root2a(p) x 2a(p)) as a consequence of the tilting of the TiO6 octahedra. Ordering of lanthanum and lithium ions and vacancies along the 2a(p)-axis, as well as displacements of titanium ions from the center of the octahedra, have been determined. The size and shape of the domains have been obtained from the synchrotron X-ray diffraction data; in addition, other extended defects such as strains and compositional fluctuations have been detected.