With the aim to improve the ionic conductivity of perovskite materials used for all-solid-state batteries, La(2/3) - xLi3xTiO3 with x = 0.11 (LLT011) ceramics was prepared by a double mechanical alloying method. The influence of thermal treatments (furnace-cooling, SC and quenching, QC) on the crystalline structure and Li-ion conductive properties of the LLTO ceramics has been studied by X-ray powder diffraction (XRD), Raman scattering and impedance spectroscopy. XRD patterns of SC-samples exhibited a doubled perovskite with a tetragonal structure, whereas those of quenched samples indicated a simple cubic perovskite. The increase in the ionic conductivity of the LLT011 ceramics was attributed to the disordered morphology that has promoted 3D-conductive mechanism. At room temperature, the grain and grain-boundary conductivities of the quenched LLT011 ceramics reached values as large as 1.8 x 10(-3) S.cm(-1) and 7.2 x 10(-5) S.cm(-1), respectively. All-solid-state batteries made from the LLT011 solid-state electrolyte combining with LiMn2O4, and SnO2 thin films as cathode and anode, respectively, possessed a charge-discharge efficiency of similar to 61% and a charging capacity of similar to 3.0 mu Ah/(cm(2) . mu m) at a voltage of 1.6 V. (C) 2015 Elsevier B.V. All rights reserved.