Garnet-like Li5La3Bi2O12 powders with particle size of 80-100 nm were prepared by the Pechini method using lithium carbonate, bismuth nitrate, and lanthanum nitrate as precursors, and high density Li5La3Bi2O12 ceramics were synthesized at 1023 K from these powders. The lowest temperature to synthesize the pure garnet-like Li5La3Bi2O12 phase is only 923 K by the Pechini method, 125 K lower than that in the solid state reaction method, and the reaction time in the Pechini method (similar to 5 h) is much shorter than that in the solid state reaction route (similar to 48 h). The total (bulk plus grain boundary) conductivity of polycrystalline Li5La3Bi2O12 ceramics prepared by the Pechini method was as high as 2.4 x 10(-5) S/cm at room temperature with an activation energy of 0.40 eV. The Li5La3Bi2O12 compounds were chemically stable against the widely used cathode materials LiCoO2 up to 873 K but not chemically stable against the LiMn2O4 if the temperature is higher than 673 K. (C) 2010 Elsevier B.V. All rights reserved.