The structure, thermal stability, morphology and ion conductivity of titanium perovskites with the general formula Li3xLn 2/3-xTiO3 (Ln=rare earth element; 3x=0.30) are studied in the context of their possible use as solid electrolyte materials for lithium ion batteries. Materials are prepared by a glycine-nitrate method using different sintering treatments, with a cation-disorder-induced structural transition from tetragonal to cubic symmetry, and are detected as quenching temperature increases. SEM images show that the average grain size increases with increasing sintering temperature and time. Slightly higher bulk conductivity values have been observed for quenched samples sintered at high temperature. Bulk conductivity decreases with the lanthanide ion size. A slight conductivity enhancement, always limited by grain boundaries, is observed for longer sintering times. TDX measurements of the electrolyte/cathode mixtures also show a good stability of the electrolytes in the temperature range of 30-1100 °C. © 2014 Elsevier Ltd and Techna Group S.r.l.