The garnet Li₇La₃Zr₂O₁₂ (LLZO) has been widely investigated because of its high conductivity, wide electrochemical window and chemical stability to lithium metal. However, the usual preparation process of LLZO requires a long time of high-temperature sintering and a lot of mother powders against the lithium evaporation. The submicron Li₆.6La₃Zr₁.6Nb₀.4O₁₂ (LLZNO) powders are prepared by conventional solid-state reaction method and attrition milling process, which are stable cubic phase and have high sintering activity, and Li stoichiometric LLZNO ceramics are obtained by sintering at a relative lower temperature or for a short time by using these powders which are difficult to control under high sintering temperature and long sintering time. The particle size distribution, phase structure, microstructure, distribution of element, total ionic conductivity, relative density and activation energy of submicron LLZNO powders and LLZNO ceramics are tested and analyzed by laser diffraction particle size analyzer, XRD, SEM, EIS and Archimedean method. The total ionic conductivity of sample sintered at 1200 °C for 30 min is 5.09 × 10-4 S·cm-1, the activation energy is 0.311 eV, and the relative density is 87.3%, and sintered at 1150 °C for 60 min total ionic conductivity is 3.49 × 10-4 S·cm-1, the activation energy is 0.316 eV, and the relative density is 90.4%. At the same time, all-solid-state batteries are assembled with LiMn₂O₄ as positive electrode and submicron LLZNO powders as solid state electrolyte. After 50 cycles, the discharge specific capacity is 105.5 mAh/g and the columbic efficiency is above 95%.