Abstract: High lithium ion conductive garnet-type barium lanthanum lithium tantalate, Li6BaLa2Ta2O12 (LLBTO), was prepared by a modified sol–gel Pechini method from the appropriate mixtures of lithium carbonate, lanthanum oxide, barium carbonate and tantalum ethoxide. The thermal decomposition of the precursor powder was investigated by TG/DTA analysis. The LLBTO precursor powders were annealed at various temperatures between 923 and 1123K for 6h in air. The transformation process from precursor powder to crystalline garnet-like phase was analyzed by X-ray powder diffraction (XRPD). The morphology of the powders annealed at various temperatures was investigated by scanning electron microscopy (SEM). The resultant pelletized Li6BaLa2Ta2O12, prepared by sol–gel synthesis method, shows a total Li-ion conductivity of 1.69×10−5 S/cm at 298K and an activation energy is 0.40eV. The ionic conductivities reported in this study are slightly higher than those reported for LLBTO sample synthesized by conventional solid state synthesis route. [Copyright &y& Elsevier]