AbstractGarnet-type Li₇La₃Zr₂O₁₂ (LLZO) solid electrolytes (SE) demonstrates appealing ionic conductivity properties for all-solid-state lithium metal battery applications. However, LLZO (electro)chemical stability in contact with the lithium metal electrode is not satisfactory for developing practical batteries. To circumvent this issue, we report the preparation of various doped cubic-phase LLZO SEs without vacancy formation (i.e., Li = 7.0 such as Li₇La₃Zr_0.5Hf_0.5Sc_0.5Nb_0.5O₁₂ and Li₇La₃Zr_0.4Hf_0.4Sn_0.4Sc_0.4Ta_0.4O₁₂). The entropy-driven synthetic approach allows access to hidden chemical space in cubic-phase garnet and enables lower solid-state synthesis temperature as the cubic-phase nucleation decreases from 750 to 400 °C. We demonstrate that the SEs with Li = 7.0 show better reduction stability against lithium metal compared to SE with low lithium contents and identical atomic species (i.e., Li = 6.6 such as Li_6.6La₃Zr_0.4Hf_0.4Sn_0.4Sc_0.2Ta_0.6O₁₂). Moreover, when a Li₇La₃Zr_0.4Hf_0.4Sn_0.4Sc_0.4Ta_0.4O₁₂ pellet is tested at 60 °C in coin cell configuration with a Li metal negative electrode, a LiNi_1/3Co_1/3Mn_1/3O₂-based positive electrode and an ionic liquid-based electrolyte at the cathode|SE interface, discharge capacity retention of about 92% is delivered after 700 cycles at 0.8 mA/cm² and 60 °C.